Means for increasing the molecular weight and decreasing the density employing mixed homogeneous catalyst formulations

ABSTRACT

A continuous solution polymerization process is disclosed wherein at least two homogeneous catalyst formulations are employed. A first homogeneous catalyst formulation is employed in a first reactor to produce a first ethylene interpolymer and a second homogeneous catalyst formulation is employed in a second reactor to produce a second ethylene interpolymer. Optionally a third ethylene interpolymer is formed in a third reactor. The resulting ethylene interpolymer products possess desirable properties in a variety of end use applications, for example in film applications. A means for increasing the molecular weight of the first ethylene interpolymer is disclosed and/or a means for increasing the temperature of the first reactor, relative to the third homogeneous catalyst formulation. A means for reducing the (α-olefin/ethylene) weight ratio in the first reactor is disclosed and/or reducing the density of the first ethylene interpolymer, relative to the third homogeneous catalyst formulation.

BACKGROUND

Solution polymerization processes are typically carried out attemperatures that are above the melting point of the ethylenehomopolymer or copolymer product. In a typical solution polymerizationprocess, catalyst components, solvent, monomers and hydrogen are fedunder pressure to one or more reactors.

For ethylene polymerization, or ethylene copolymerization, reactortemperatures can range from about 80° C. to about 300° C. whilepressures generally range from about 3 MPag to about 45 MPag. Theethylene homopolymer or copolymer produced remains dissolved in thesolvent under reactor conditions. The residence time of the solvent inthe reactor is relatively short, for example, from about 1 second toabout 20 minutes. The solution process can be operated under a widerange of process conditions that allow the production of a wide varietyof ethylene polymers. Post reactor, the polymerization reaction isquenched to prevent further polymerization, by adding a catalystdeactivator. Optionally, if a heterogeneous catalyst formulation isemployed in the third reactor, the deactivated solution is passivated,by adding an acid scavenger. The deactivated solution, or optionally thepassivated solution, is then forwarded to polymer recovery where theethylene homopolymer or copolymer is separated from process solvent,unreacted residual ethylene and unreacted optional α-olefin(s).

There is a need to improve the continuous solution polymerizationprocess, for example, to increase the molecular weight of the ethyleneinterpolymer produced at a given reactor temperature. Given a specificcatalyst formulation, it is well known to those of ordinary experiencethat polymer molecular weight increases as reactor temperaturedecreases. However, decreasing reactor temperature can be problematicwhen the viscosity of the solution becomes too high. As a result, in thesolution polymerization process there is a need for catalystformulations that produce high molecular weight ethylene interpolymersat high reactor temperatures. The catalyst formulations and solutionpolymerization processes disclosed herein satisfy this need.

In the solution polymerization process there is also a need for catalystformulations that are very efficient at incorporating one or moreα-olefins into a propagating macromolecular chain. In other words, at agiven [α-olefin/ethylene] weight ratio in a solution polymerizationreactor, there is a need for catalyst formulations that produce lowerdensity ethylene/α-olefin copolymers. Expressed alternatively, there isa need for catalyst formulations that produce an ethylene/α-olefincopolymer, having a specific density, at a lower (α-olefin/ethylene)ratio in the reactor feed. Such catalyst formulations efficientlyutilize the available α-olefin and reduce the amount of α-olefin insolution process recycle streams.

The catalyst formulations and solution process disclosed herein, produceunique ethylene interpolymer products that have desirable properties ina variety of end use applications, for example applications that employethylene interpolymer films. Non-limiting examples of desirable filmproperties include higher film stiffness, higher film tensile yield,higher film tear resistance, lower hexane extractables, lower sealinitiation temperature and improved hot tack performance. Films preparedfrom the ethylene interpolymer products, disclosed herein, have thesedesirable properties.

SUMMARY OF DISCLOSURE

One embodiment of this disclosure is an ethylene interpolymer productcomprising: (i) a first ethylene interpolymer; (ii) a second ethyleneinterpolymer, and; (iii) optionally a third ethylene interpolymer: wherethe ethylene interpolymer product has a dimensionless Long ChainBranching Factor (LCBF) greater than or equal to about 0.001; from about0.0015 ppm to about 2.4 ppm of hafnium, and; from about 0.006 ppm toabout 5.7 ppm of titanium.

Additional embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer: where the ethylene interpolymer product has adimensionless Long Chain Branching Factor (LCBF) greater than or equalto about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; fromabout 0.006 ppm to about 5.7 ppm of titanium, and; less than or equal toabout 0.01 terminal vinyl unsaturations per 100 carbon atoms.

Additional embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer: where the ethylene interpolymer product has adimensionless Long Chain Branching Factor (LCBF) greater than or equalto about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; fromabout 0.006 ppm to about 5.7 ppm of titanium and; from about 0.03 ppm toabout 6.0 ppm of total catalytic metal.

Further embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer: where the ethylene interpolymer product has adimensionless Long Chain Branching Factor (LCBF) greater than or equalto about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; fromabout 0.006 ppm to about 5.7 ppm of titanium; less than or equal toabout 0.01 terminal vinyl unsaturations per 100 carbon atoms, and; fromabout 0.03 ppm to about 6.0 ppm of total catalytic metal.

Embodiment of this disclosure include ethylene interpolymer productscomprising: (i) a first ethylene interpolymer; (ii) a second ethyleneinterpolymer, and; (iii) optionally a third ethylene interpolymer: wherethe ethylene interpolymer product has a dimensionless Long ChainBranching Factor (LCBF) greater than or equal to about 0.001; from about0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm to about5.7 ppm of titanium; less than or equal to about 0.01 terminal vinylunsaturations per 100 carbon atoms, and; from about 0.03 ppm to about6.0 ppm of total catalytic metal.

Embodiments of this disclosure include ethylene interpolymer productshaving a melt index from about 0.3 to about 500 dg/minute. Furtherembodiments include ethylene interpolymer products having a density fromabout 0.855 to about 0.975 g/cc. Other embodiments include ethyleneinterpolymer products having a M_(w)/M_(n) from about 1.7 to about 25.Embodiments include ethylene interpolymer products having a CDBI₅₀(Composition Distribution Breadth Index) from about 1% to about 98%.

Embodiments include ethylene interpolymer products containing 5 to 60 wt% of a first ethylene interpolymer, 20 to 95 wt % of a second ethyleneinterpolymer and 0 to 30 wt % of a third ethylene interpolymer; where wt% is the weight of the first, the second or the optional third ethyleneinterpolymer, individually, divided by the total weight of the ethyleneinterpolymer product. Additional embodiments include ethyleneinterpolymer products where the first ethylene interpolymer has a meltindex from about 0.01 to about 200 dg/minute, the second ethyleneinterpolymer has melt index from about 0.3 to about 1000 dg/minute, andthe third ethylene interpolymer has a melt index from about 0.5 to about2000 dg/minute. Other embodiments include ethylene interpolymer productswhere the first ethylene interpolymer has a density from about 0.855g/cm³ to about 0.975 g/cc, the second ethylene interpolymer has adensity from about 0.855 g/cm³ to about 0.975 g/cc, and the thirdethylene interpolymer has density from about 0.855 g/cm³ to about 0.975g/cc.

Embodiments include ethylene interpolymer products containing from 0 to10 mole percent of one or more α-olefin, where the α-olefins are C₃ toC₁₀ α-olefins. Non-limiting examples include ethylene interpolymerproducts containing the following α-olefins: 1-octene, 1-hexene or amixture of 1-octene and 1-hexene.

Embodiments of this disclosure include a first ethylene interpolymersynthesized using at least one homogeneous catalyst formulation.Additional embodiments include the synthesis of a first ethyleneinterpolymer using a first homogeneous catalyst formulation. Onenon-limiting example of the first homogeneous catalyst formulation is abridged metallocene catalyst formulation containing a component Adefined by Formula (I)

Embodiments of this disclosure include a second ethylene interpolymersynthesized using a second homogeneous catalyst formulation.Non-limiting examples of the second homogeneous catalyst formulationinclude an unbridged single site catalyst formulation.

Optional embodiments include the synthesis of a third ethyleneinterpolymer using a heterogeneous catalyst formulation. Furtheroptional embodiments include the synthesis of the third ethyleneinterpolymer using a fifth homogeneous catalyst formulation. The fifthhomogeneous catalyst formulation may be: a bridged metallocene catalystformulation, an unbridged single site catalyst formulation or a fourthhomogeneous catalyst formulation. The fourth homogeneous catalystformulation contains a bulky ligand-metal complex that is not a memberof the chemical genera that defines: a) the bulky ligand-metal complexemployed in the bridged metallocene catalyst formulation, and; b) thebulky ligand-metal complex employed in the unbridged single sitecatalyst formulation.

Embodiments of this disclosure include ethylene interpolymer productscontaining a catalytic metal A that may range from about 2.4 ppm toabout 0.0015 ppm, where catalytic metal A originates from the firsthomogeneous catalyst formulation. Ethylene interpolymer products mayalso contain a catalytic metal C that may range from about 2.9 ppm toabout 0.006 ppm, where catalytic metal C originates from the secondhomogeneous catalyst formulation. Non-limiting examples of metals A andC include titanium, zirconium and hafnium. Optionally, ethyleneinterpolymer products may contain a metal D that may range from 0.9 ppmto 0 ppm; where catalytic metal D originates from the fourth homogeneouscatalyst formulation. Non-limiting examples of metal D include titanium,zirconium and hafnium. Additional optional embodiments include ethyleneinterpolymer products that contain a catalytic metal Z that may rangefrom about 3.9 ppm to about 0 ppm; where catalytic metal Z originatesfrom a heterogeneous catalyst formulation. Non-limiting examples ofcatalytic metal Z includes: titanium, zirconium, hafnium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, manganese,technetium, rhenium, iron, ruthenium or osmium.

Embodiments of the disclosed ethylene interpolymer products contain afirst ethylene interpolymer having a first M_(w)/M_(n) from about 1.7 toabout 2.8, a second ethylene interpolymer having a second M_(w)/M_(n)from about 1.7 to about 2.8 and an optional third ethylene interpolymerhaving a third M_(w)/M_(n) from about 1.7 to about 5.0.

Further embodiments of the ethylene interpolymer products contain afirst ethylene interpolymer having a first CDBI₅₀ from about 70 to about98%, a second ethylene interpolymer having a second CDBI₅₀ from about 70to about 98% and an optional third ethylene interpolymer having a thirdCDBI₅₀ from about 35 to about 98%. This disclosure includes embodimentof a continuous solution polymerization process where a first and asecond reactor are operated in series mode (i.e. the effluent from thefirst reactor flows into the second reactor), a first homogeneouscatalyst formulation is employed in the first reactor and a secondhomogeneous catalyst formulations is employed in the second reactor;optionally a heterogeneous catalyst formulation or a fifth homogeneouscatalyst formulation is employed in an optional third reactor. Thisembodiment of a continuous solution polymerization process comprises: i)injecting ethylene, a process solvent, a first homogeneous catalystformulation, optionally one or more α-olefins and optionally hydrogeninto a first reactor to produce a first exit stream containing a firstethylene interpolymer in process solvent; ii) passing the first exitstream into a second reactor and injecting into the second reactor,ethylene, process solvent, a second homogeneous catalyst formulation,optionally one or more α-olefins and optionally hydrogen to produce asecond exit stream containing a second ethylene interpolymer and thefirst ethylene interpolymer in process solvent; iii) passing the secondexit stream into a third reactor and optionally injecting into the thirdreactor, ethylene, process solvent, one or more α-olefins, hydrogen anda fifth homogeneous catalyst formulation and/or a heterogeneous catalystformulation to produce a third exit stream containing an optional thirdethylene interpolymer, the second ethylene interpolymer and the firstethylene interpolymer in process solvent; iv) phase separating the thirdexit stream to recover an ethylene interpolymer product comprising thefirst ethylene interpolymer, the second ethylene interpolymer and theoptional third ethylene interpolymer. The solution process, series modeembodiments, were improved by having a lower [α-olefin/ethylene] weightratio in the first reactor and/or the first reactor produces a highermolecular first ethylene interpolymer. In some embodiments, thedisclosed solution process had at least an 70% improved (reduced)[α-olefin/ethylene] weight ratio as defined by the following formula

${\%\mspace{14mu}{{Reduced}\left\lbrack \frac{\alpha\text{-}{olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$where (α-olefin/ethylene)^(A) was calculated by dividing the weight ofα-olefin added to the first reactor by the weight of ethylene added tothe first reactor where a first ethylene interpolymer having a targetdensity was produced by the first homogeneous catalyst formulation, and;(α-olefin/ethylene)^(C) was calculated by dividing the weight ofα-olefin added to the first reactor by the weight of ethylene added tothe first reactor where a control ethylene interpolymer having thetarget density was produced by replacing the first homogeneous catalystformulation with a third homogeneous catalyst formulation. In otherembodiments of the solution polymerization process had at least a 5%improved weight average molecular weight as defined by the followingformula% Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5%where M_(w) ^(A) was the weight average molecular weight of the firstethylene interpolymer and M_(w) ^(C) was the weight average molecularweight of a comparative ethylene interpolymer; where the comparativeethylene interpolymer was produced in the first reactor by replacing thefirst homogeneous catalyst formulation with the third homogeneouscatalyst formulation.

In another embodiment of the continuous solution polymerization processthe first and second reactors are operated in parallel mode, i.e. thefirst exit stream (exiting the first reactor) by-passes the secondreactor and the first exit stream is combined with the second exitstream (exiting the second reactor) downstream of the second reactor.Parallel mode embodiments comprises: i) injecting ethylene, a processsolvent, a first homogeneous catalyst formulation, optionally one ormore α-olefins and optionally hydrogen into a first reactor to produce afirst exit stream containing a first ethylene interpolymer in processsolvent; ii) injecting ethylene, process solvent, a second homogeneouscatalyst formulation, optionally one or more α-olefins and optionallyhydrogen into a second reactor to produce a second exit streamcontaining a second ethylene interpolymer in process solvent; iii)combining the first and second exit streams to form a third exit stream;iv) passing the third exit stream into a third reactor and optionallyinjecting into the third reactor, ethylene, process solvent, one or moreα-olefins, hydrogen and a fifth homogeneous catalyst formulation and/ora heterogeneous catalyst formulation to produce a fourth exit streamcontaining an optional third ethylene interpolymer, the second ethyleneinterpolymer and the first ethylene interpolymer in said processsolvent; v) phase separating the fourth exit stream to recover anethylene interpolymer product comprising the first ethyleneinterpolymer, the second ethylene interpolymer and the optional thirdethylene interpolymer. Parallel mode embodiment were improved by havinga lower [α-olefin/ethylene] weight ratio in the first reactor and/or ahigher molecular first ethylene interpolymer, as characterized by theseries mode embodiments described immediately above.

Additional embodiments of the series and parallel solutionpolymerization processes include the post reactor addition of a catalystdeactivator to neutralize or deactivate the catalysts, forming adeactivated solution. If a heterogeneous catalyst formulation wasemployed in the third reactor, the continuous solution polymerizationprocess included an additional step where a passivator was added to thedeactivated solution, forming a passivated solution. Additionalembodiments included steps where the catalyst inlet temperature wasadjusted to optimize the activity of the bridged metallocene catalystformulation.

The disclosed solution polymerization processes include embodimentswhere the heterogeneous catalyst formulation was a Ziegler-Nattacatalyst formulation prepared using an in-line process, hereinafter ‘thein-line Ziegler-Natta catalyst formulation’. In alternative embodimentsthe heterogeneous catalyst formulation was a Ziegler-Natta catalystformulation prepared using a batch process, hereinafter ‘the batchZiegler-Natta catalyst formulation’.

Further embodiments include the solution process synthesis of anethylene interpolymer product that includes a means for reducing, by atleast −70%, the [α-olefin/ethylene] weight ratio required to produce thefirst ethylene interpolymer (in the ethylene interpolymer product),where the first ethylene interpolymer has a target density; the meansinvolves the appropriate selection of the catalyst formulation employedin the first reactor.

Further embodiments include the synthesis of a solution process ethyleneinterpolymer product that includes a means for increasing, by at least5%, the weight average molecular weight (M_(w)) of the first ethyleneinterpolymer (in the ethylene interpolymer product); the means involvesthe appropriate selection of the catalyst formulation employed in thefirst reactor.

Further embodiments of the present disclosure include manufacturedarticles; non-limiting examples of manufactured articles includeflexible articles such as films and rigid articles such a containers.

Manufactured articles embodiments include a polyethylene film comprisingat least one layer, where the layer comprises at least one of theethylene interpolymer products disclosed herein. Such films had amachine direction 1% secant modulus that was improved (by at least 25%)and a transverse direction 1% secant modulus that was improved (by atleast 50% higher); relative to a comparative polyethylene film of thesame composition but the first ethylene interpolymer (in the ethyleneinterpolymer product) was replaced with a comparative ethyleneinterpolymer, where the first ethylene interpolymer was produced with abridged metallocene catalyst formulation and the comparative ethyleneinterpolymer was produced with an unbridged single site catalystformulation. Film examples also had improved machine direction 2% secantmodulus (by at least 25%) and an improved transverse direction 2% secantmodulus (by at least 50%); relative to a film produced from thecomparative ethylene interpolymer. Further film embodiments had animproved machine direction tensile yield (by at least 10%) and animproved transverse direction tensile yield (by at least 30%); relativeto the film produced from the comparative ethylene interpolymer. Filmsdisclosed herein had improved (lower) hexane extractables, i.e. theamount of hexane soluble material (weight %) extracted from filmscontaining the ethylene interpolymer product was about 50% lower,relative to films prepared from the comparative ethylene interpolymer.Additional film embodiments had improved (lower) seal initiationtemperature (at least 5% lower), relative to films prepared fromcomparative ethylene interpolymers. The hot tack performance of filmsprepared from the disclosed ethylene interpolymer products were alsoimproved; e.g., the temperature at the onset of film Tack (at a force of1.0N) was improved (lower by about 10%), relative to a comparativepolyethylene film of the same composition but said first ethyleneinterpolymer (in the ethylene interpolymer product) was replaced with acomparative ethylene interpolymer; where the first ethylene interpolymerwas produced with a bridged metallocene catalyst formulation and thecomparative ethylene interpolymer was produced with an unbridged singlesite catalyst formulation. Films disclosed herein also had improved dartimpact. For example, the dart impact of a film prepared from an ethyleneinterpolymer product was about 100% higher, relative to a film preparedfrom the comparative ethylene interpolymer.

Further embodiments include polyethylene films comprising at least onelayer, where the layer comprises at least one ethylene interpolymerproduct and at least one second polymer. Non-limiting examples of secondpolymers include ethylene polymers, propylene polymers or a mixture ofethylene polymers and propylene polymers.

Additional embodiments include a polyethylene films having a thicknessfrom about 0.5 mil to about 10 mil. Embodiments also include multilayerfilms comprises from 2 to 11 layers, where at least one layer comprisesat least one of the ethylene interpolymer products disclosed herein.

BRIEF DESCRIPTION OF FIGURES

The following Figures are presented for the purpose of illustratingselected embodiments of this disclosure; it being understood, that theembodiments in this disclosure are not limited to the precisearrangement of, or the number of, vessels shown.

FIG. 1 shows the determination of the Long Chain Branching Factor(LCBF). The abscissa plotted was the log of the corrected Zero ShearViscosity (log(ZSV_(c))) and the ordinate plotted was the log of thecorrected Intrinsic Viscosity (log(IV_(c))). Ethylene polymers that donot have LCB, or undetectable LCB, fall on the reference line. Ethylenepolymers having LCB deviate from the reference line and werecharacterized by the dimensionless Long Chain Branching Factor (LCBF).LCBF=(S_(h)×S_(v))/2; where S_(h) and S_(v) are horizontal and verticalshift factors, respectively.

FIG. 2 illustrates a continuous solution polymerization process where afirst homogeneous catalyst formulation and a second homogeneous catalystformulation were employed in reactors 11 a and 12 a, respectively.Optionally (dotted lines) an in-line Ziegler-Natta catalyst formulationor a batch Ziegler-Natta catalyst formulation was employed in reactor17.

FIG. 3 illustrates the nomenclature used to identify various carbonatoms that give rise to signals in ¹³C NMR spectra.

FIG. 4 deconvolution of ethylene interpolymer product Example 51 into afirst, second and third ethylene interpolymer.

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” is used to describe a monomer havinga linear hydrocarbon chain containing from 3 to 20 carbon atoms having adouble bond at one end of the chain; an equivalent term is “linearα-olefin”.

As used herein, the term “ethylene polymer”, refers to macromoleculesproduced from ethylene monomers and optionally one or more additionalmonomers; regardless of the specific catalyst or specific process usedto make the ethylene polymer. In the polyethylene art, the one or moreadditional monomers are called “comonomer(s)” and often includeα-olefins. The term “homopolymer” refers to a polymer that contains onlyone type of monomer. Common ethylene polymers include high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE), very low density polyethylene (VLDPE),ultralow density polyethylene (ULDPE), plastomer and elastomers. Theterm ethylene polymer also includes polymers produced in a high pressurepolymerization processes; non-limiting examples include low densitypolyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylenealkyl acrylate copolymers, ethylene acrylic acid copolymers and metalsalts of ethylene acrylic acid (commonly referred to as ionomers). Theterm ethylene polymer also includes block copolymers which may include 2to 4 comonomers. The term ethylene polymer also includes combinationsof, or blends of, the ethylene polymers described above.

The term “ethylene interpolymer” refers to a subset of polymers withinthe “ethylene polymer” group that excludes polymers produced in highpressure polymerization processes; non-limiting examples of polymerproduced in high pressure processes include LDPE and EVA (the latter isa copolymer of ethylene and vinyl acetate).

The term “heterogeneous ethylene interpolymers” refers to a subset ofpolymers in the ethylene interpolymer group that are produced using aheterogeneous catalyst formulation; non-limiting examples of whichinclude Ziegler-Natta or chromium catalysts.

The term “homogeneous ethylene interpolymer” refers to a subset ofpolymers in the ethylene interpolymer group that are produced usinghomogeneous catalyst formulations. Typically, homogeneous ethyleneinterpolymers have narrow molecular weight distributions, for exampleSize Exclusion Chromatography (SEC) M_(w)/M_(n) values of less than 2.8;M_(w) and M_(n) refer to weight and number average molecular weights,respectively. In contrast, the M_(w)/M_(n) of heterogeneous ethyleneinterpolymers are typically greater than the M_(w)/M_(n) of homogeneousethylene interpolymers. In general, homogeneous ethylene interpolymersalso have a narrow comonomer distribution, i.e. each macromoleculewithin the molecular weight distribution has a similar comonomercontent. Frequently, the composition distribution breadth index “CDBI”is used to quantify how the comonomer is distributed within an ethyleneinterpolymer, as well as to differentiate ethylene interpolymersproduced with different catalysts or processes. The “CDBI₅₀” is definedas the percent of ethylene interpolymer whose composition is within 50%of the median comonomer composition; this definition is consistent withthat described in U.S. Pat. No. 5,206,075 assigned to Exxon ChemicalPatents Inc. The CDBI₅₀ of an ethylene interpolymer can be calculatedfrom TREF curves (Temperature Rising Elution Fractionation); the TREFmethod is described in Wild, et al., J. Polym. Sci., Part B, Polym.Phys., Vol. 20 (3), pages 441-455. Typically the CDBI₅₀ of homogeneousethylene interpolymers are greater than about 70%. In contrast, theCDBI₅₀ of α-olefin containing heterogeneous ethylene interpolymers aregenerally lower than the CDBI₅₀ of homogeneous ethylene interpolymers. Ablend of two or more homogeneous ethylene interpolymers, that differ incomonomer content, may have a CDBI₅₀ less than 70%; in this disclosuresuch a blend was defined as a homogeneous blend or homogeneouscomposition. Similarly, a blend of two or more homogeneous ethyleneinterpolymers, that differ in weight average molecular weight (M_(w)),may have a M_(w)/M_(n)≥2.8; in this disclosure such a blend was definedas a homogeneous blend or homogeneous composition.

In this disclosure, the term “homogeneous ethylene interpolymer” refersto both linear homogeneous ethylene interpolymers and substantiallylinear homogeneous ethylene interpolymers. In the art, linearhomogeneous ethylene interpolymers are generally assumed to have no longchain branches or an undetectable amount of long chain branches; whilesubstantially linear ethylene interpolymers are generally assumed tohave greater than about 0.01 to about 3.0 long chain branches per 1000carbon atoms. A long chain branch is macromolecular in nature, i.e.similar in length to the macromolecule that the long chain branch isattached to.

In this disclosure the term homogeneous catalyst is used, for example todescribe a first, a second, a third, a fourth and a fifth homogeneouscatalyst formulation. The term catalyst refers to the chemical compoundcontaining the catalytic metal, which is a metal-ligand complex. In thisdisclosure, the term ‘homogeneous catalyst’ is defined by thecharacteristics of the polymer produced by the homogeneous catalyst.Specifically, a catalyst is a homogeneous catalyst if it produces ahomogeneous ethylene interpolymer that has a narrow molecular weightdistribution (SEC M_(w)/M_(n) values of less than 2.8) and a narrowcomonomer distribution (CDBI₅₀>70%). Homogeneous catalysts are wellknown in the art. Two subsets of the homogeneous catalyst genus includeunbridged metallocene catalysts and bridged metallocene catalysts.Unbridged metallocene catalysts are characterized by two bulky ligandsbonded to the catalytic metal, a non-limiting example includesbis(isopropyl-cyclopentadienyl) hafnium dichloride. In bridgedmetallocene catalysts the two bulky ligands are covalently bonded(bridged) together, a non-limiting example includes diphenylmethylene(cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium dichloride; whereinthe diphenylmethylene group bonds, or bridges, the cyclopentadienyl andfluorenyl bulky ligands together. Two additional subsets of thehomogeneous catalyst genus include unbridged and bridged single sitecatalysts. In this disclosure, single site catalysts are characterizedas having only one bulky ligand bonded to the catalytic metal. Anon-limiting example of an unbridged single site catalyst includescyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride. Anon-limiting example of a bridged single site catalyst includes[C₅(CH₃)₄—Si(CH₃)₂—N(tBu)] titanium dichloride, where the —Si(CH₃)₂—group functions as the bridging group.

Herein, the term “polyolefin” includes ethylene polymers and propylenepolymers; non-limiting examples of propylene polymers include isotactic,syndiotactic and atactic propylene homopolymers, random propylenecopolymers containing at least one comonomer (e.g. α-olefins) and impactpolypropylene copolymers or heterophasic polypropylene copolymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers used in theplastic industry; non-limiting examples of other polymers commonly usedin film applications include barrier resins (EVOH), tie resins,polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear, branched, or cyclic, aliphatic,olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogenand carbon that are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms selected from the groupconsisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur. Non-limiting examples ofheteroatom-containing groups include radicals of imines, amines, oxides,phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines,thioethers, and the like. The term “heterocyclic” refers to ring systemshaving a carbon backbone that comprise from 1 to 3 atoms selected fromthe group consisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include: acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

Herein the term “R1” and its superscript form “^(R1)” refers to a firstreactor in a continuous solution polymerization process; it beingunderstood that R1 is distinctly different from the symbol R¹; thelatter is used in chemical formula, e.g. representing a hydrocarbylgroup. Similarly, the term “R2” and it's superscript form “^(R2)” refersto a second reactor, and; the term “R3” and it's superscript form“^(R3)” refers to a third reactor.

As used herein, the term “oligomers” refers to an ethylene polymer oflow molecular weight, e.g., an ethylene polymer with a weight averagemolecular weight (M_(w)) of about 2000 to 3000 daltons. Other commonlyused terms for oligomers include “wax” or “grease”. As used herein, theterm “light-end impurities” refers to chemical compounds with relativelylow boiling points that may be present in the various vessels andprocess streams within a continuous solution polymerization process;non-limiting examples include, methane, ethane, propane, butane,nitrogen, CO₂, chloroethane, HCl, etc.

DETAILED DESCRIPTION

Catalysts

Catalyst formulations that are efficient in polymerizing olefins arewell known. In the embodiments disclosed herein, at least two catalystformulations were employed in a continuous solution polymerizationprocess. One of the catalyst formulations comprised a first homogeneouscatalyst formulation that produces a homogeneous first ethyleneinterpolymer in a first reactor, one embodiment of the first homogeneouscatalyst formulation was a bridged metallocene catalyst formulation(Formula (I)). The other catalyst formulation comprised a secondhomogeneous catalyst formulation that produced a second ethyleneinterpolymer in a second reactor, one embodiment of the secondhomogeneous catalyst formulation was an unbridged single site catalystformulation (Formula (II)). Optionally a third ethylene interpolymer maybe produced in a third reactor using one or more of: the first, thesecond, a third homogeneous catalyst formulation, a fifth homogeneouscatalyst formulation or a heterogeneous catalyst formulation. Oneembodiment of the third homogeneous catalyst formulation was anunbridged single site catalyst formulation (Formula (II)). The fifthhomogeneous catalyst formulation was selected from the first, thesecond, the third and/or a fourth homogeneous catalyst formulation;where the fourth homogeneous catalyst formulation contains a bulkyligand-metal complex that was not a species of the chemical generadefined by Formula (I) or Formula (II). In the continuous solutionprocess disclosed, at least two homogeneous ethylene interpolymers wereproduced and solution blended to produce an ethylene interpolymerproduct.

Bulky Ligand-Metal Complexes

Component A

The present disclosure included “a first homogeneous catalystformulation”. One embodiment of the first homogeneous catalystformulation was “a bridged metallocene catalyst formulation” containinga bulky ligand-metal complex, hereinafter “component A”, represented byFormula (I).

In Formula (I): non-limiting examples of M include Group 4 metals, i.e.titanium, zirconium and hafnium; non-limiting examples of G includeGroup 14 elements, carbon, silicon, germanium, tin and lead; Xrepresents a halogen atom, fluorine, chlorine, bromine or iodine; the R6groups are independently selected from a hydrogen atom, a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxideradical (these radicals may be linear, branched or cyclic or furthersubstituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxyradicals, C₆₋₁₀ aryl or aryloxy radicals); R₁ represents a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀aryl oxide radical; R₂ and R₃ are independently selected from a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀aryl oxide radical, and; R₄ and R₅ are independently selected from ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or aC₆₋₁₀ aryl oxide radical.

In the art, a commonly used term for the X(R₆) group shown in Formula(I) is “leaving group”, i.e. any ligand that can be abstracted fromFormula (I) forming a catalyst species capable of polymerizing one ormore olefin(s). An equivalent term for the X(R₆) group is an“activatable ligand”. Further non-limiting examples of the X(R₆) groupshown in Formula (I) include weak bases such as amines, phosphines,ethers, carboxylates and dienes. In another embodiment, the two R₆groups may form part of a fused ring or ring system.

Further embodiments of component A include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof ofthe structure shown in Formula (I).

In this disclosure, various species of component A (Formula (I)) weredenoted by the terms “component A1”, “component A2” and “component A3”,etc. While not to be construed as limiting, two species of component Awere employed as examples in this disclosure. Specifically: “componentA1” refers todiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂],and; “component A2” refers todiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]. Inthis disclosure, component A1 and component A2 were used to prepareexamples of the bridged metallocene catalyst formulation.

Long Chain Branching in Ethylene Interpolymer Products (Via Component A)

In this disclosure, the first homogeneous catalyst formulation,comprising a component A, produces ethylene interpolymer products thathave long chain branches, hereinafter ‘LCB’.

LCB is a well-known structural phenomenon in polyethylenes and wellknown to those of ordinary skill in the art. Traditionally, there arethree methods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

A limitation with LCB analysis via NMR is that it cannot distinguishbranch length for branches equal to or longer than six carbon atoms(thus, NMR cannot be used to characterize LCB in ethylene/1-octenecopolymers, which have hexyl groups as side branches).

The triple detection SEC method measures the intrinsic viscosity ([η])(see W. W. Yau, D. Gillespie, Analytical and Polymer Science, TAPPIPolymers, Laminations, and Coatings Conference Proceedings, Chicago2000; 2: 699 or F. Beer, G. Capaccio, L. J. Rose, J. Appl. Polym. Sci.1999, 73: 2807 or P. M. Wood-Adams, J. M. Dealy, A. W. deGroot, O. D.Redwine, Macromolecules 2000; 33: 7489). By referencing the intrinsicviscosity of a branched polymer No to that of a linear one ([η]_(l)) atthe same molecular weight, the viscosity branching index factor g′(g′=[η]_(b)/[η]_(l)) was used for branching characterization. However,both short chain branching (SCB) and long chain branching (LCB) makecontribution to the intrinsic viscosity ([η]), effort was made toisolate the SCB contribution for ethylene/1-butene and ethylene/1-hexenecopolymers but not ethylene/1-octene copolymers (see Lue et al., U.S.Pat. No. 6,870,010 B1). In this disclosure, a systematical investigationwas performed to look at the SCB impact on the Mark-Houwink constant Kfor three types ethylene/1-olefin copolymers, i.e. octene, hexene andbutene copolymers. After the deduction of SCB contribution, a ViscosityLCB Index was introduced for the characterization of ethylene/1-olefincopolymers containing LCB. The Viscosity LCB Index was defined as themeasured Mark-Houwink constant (K_(m)) in 1,2,4-trichlorobenzene (TCB)at 140° C. for the sample divided by the SCB corrected Mark-Houwinkconstant (K_(co)) for linear ethylene/1-olefin copolymer, Eq.(1).

$\begin{matrix}{{{Viscosity}\mspace{14mu}{LCB}\mspace{14mu}{Index}} = {\frac{K_{m}}{K_{co}} = \frac{\lbrack\eta\rbrack/M_{v}^{0.725}}{\left( {391.98 - {A \times {SCB}}} \right)/1000000}}} & {{Eq}.\mspace{14mu}(1)}\end{matrix}$Where [η] was the intrinsic viscosity (dL/g) determined by 3D-SEC, M_(v)was the viscosity average molar mass (g/mole) determined using 3D-SEC;SCB was the short chain branching content (CH₃#/1000 C) determined usingFTIR, and; A was a constant which depends on the α-olefin present in theethylene/α-olefin interpolymer under test, specifically, A is 2.1626,1.9772 and 1.1398 for 1-octene, 1-hexene and 1-butene respectively. Inthe case of an ethylene homopolymer no correction is required for theMark-Houwink constant, i.e. SCB is zero.

In the art, rheology has also been an effective method to measure theamount of LCB, or lack of, in ethylene interpolymers. Severalrheological methods to quantify LCB have been disclosed. Onecommonly-used method was based on zero-shear viscosity (η₀) and weightaverage molar mass (M_(w)) data. The 3.41 power dependence (η₀=K×M_(w)^(3.41)) has been established for monodisperse polyethylene solelycomposed of linear chains, for example see R. L. Arnett and C. P.Thomas, J. Phys. Chem. 1980, 84, 649-652. An ethylene polymer with a η₀exceeding what was expected for a linear ethylene polymer, with the sameM_(w), was considered to contain long-chain branches. However, there isa debate in the field regarding the influence of polydispersity, e.g.M_(w)/M_(n). A dependence on polydispersity was observed in some cases(see M. Ansari et al., Rheol. Acta, 2011, 5017-27) but not in others(see T. P. Karjala et al., Journal of Applied Polymer Science 2011,636-646).

Another example of LCB analysis via rheology was based on zero-shearviscosity (η₀) and intrinsic viscosity ([η]) data, for example see R. N.Shroff and H. Mavridis, Macromolecules 1999, 32, 8454; which isapplicable for essentially linear polyethylenes (i.e. polyethylenes withvery low levels of LCB). A critical limitation of this method is thecontribution of the SCB to the intrinsic viscosity. It is well knownthat [η] decreases with increasing SCB content.

In this disclosure, a systematical investigation was performed to lookat the impact of both SCB and molar mass distribution. After thededuction of the contribution of both SCB and molar mass distribution(polydispersity), a Long Chain Branching Factor (LCBF) was introduced tocharacterize the amount of LCB in ethylene/α-olefin copolymers, asdescribed below.

Long Chain Branching Factor (LCBF)

In this disclosure the Long Chain Branching Factor, hereinafter LCBF,was used to characterize the amount of LCB in ethylene interpolymerproducts. The disclosed ethylene interpolymer products were in-situblends of at least two ethylene interpolymers produced with at least twodifferent catalyst formulations.

FIG. 1 illustrates the calculation of the LCBF. The solid ‘ReferenceLine’ shown in FIG. 1 characterizes ethylene polymers that do notcontain LCB (or undetectable LCB). Ethylene polymers containing LCBdeviate from this Reference Line. For example, the disclosed ethyleneinterpolymer products Examples 50-52 (the ‘+’ symbols FIG. 1) deviatehorizontally and vertically from the Reference Line. LCBF calculationrequires the polydispersity corrected Zero Shear Viscosity (ZSV_(c)) andthe SCB corrected Intrinsic Viscosity (IV_(c)) as fully described in thefollowing paragraphs.

The correction to the Zero Shear Viscosity, ZSV_(c), having dimensionsof poise, was performed as shown in equation Eq.(2):

$\begin{matrix}{{ZSV}_{c} = \frac{1.8389 \times \eta_{0}}{2.4110^{{Ln}{({Pd})}}}} & {{Eq}.\mspace{14mu}(2)}\end{matrix}$where η₀, the zero shear viscosity (poise), was measured by DMA asdescribed in the ‘Testing Methods’ section of this disclosure; Pd wasthe dimensionless polydispersity (M_(w)/M_(n)) as measured usingconventional SEC (see ‘Testing Methods’) and 1.8389 and 2.4110 aredimensionless constants.

The correction to the Intrinsic Viscosity, IV_(c), having dimensions ofdL/g, was performed as shown in equation Eq.(3):

$\begin{matrix}{{IV}_{c} = {\lbrack\eta\rbrack + \frac{A \times {SCB} \times M_{v}^{0.725}}{1000000}}} & {{Eq}.\mspace{14mu}(3)}\end{matrix}$where the intrinsic viscosity [η] (dL/g) was measured using 3D-SEC (see‘Testing Methods’); SCB having dimensions of (CH₃#/1000 C) wasdetermined using FTIR (see ‘Testing Methods’); M_(v), the viscosityaverage molar mass (g/mole), was determined using 3D-SEC (see ‘TestingMethods’), and; A was a dimensionless constant that depends on theα-olefin in the ethylene/α-olefin interpolymer sample, i.e. A was2.1626, 1.9772 or 1.1398 for 1-octene, 1-hexene and 1-butene α-olefins,respectively. In the case of an ethylene homopolymer no correction isrequired for the Mark-Houwink constant, i.e. SCB is zero.

As shown in FIG. 1, linear ethylene/α-olefin interpolymers (which do notcontain LCB or contain undetectable levels of LCB) fall on the ReferenceLine defined by Eq.(4).Log(IV_(c))=0.2100×Log(ZSV_(c))−0.7879  Eq. (4)

Table 1A shows the Reference Resins had M_(w)/M_(n) values that rangedfrom 1.68 to 9.23 and contained 1-octene, 1-hexene or 1-buteneα-olefins. Further, Reference Resins included ethylene polymers producedin solution, gas phase or slurry processes with Ziegler-Natta,homogeneous and mixed (Ziegler-Natta+homogeneous) catalyst formulations.

The ethylene interpolymer products, disclosed herein, contain long chainbranching as evidenced by Table 2 and FIG. 1. More specifically, Table 2discloses that the LCBF of Examples 50 through 52 and Example 58 were0.00845, 0.0369, 0.0484 and 0.0417, respectively. Example 50-52(+symbol) and Example 58 (open square) deviate significantly from theReference Line shown in FIG. 1. Examples 50 through 52 and Example 58were produced using a bridged metallocene catalyst formulation in thefirst reactor and an unbridged single site catalyst formulation in thesecond reactor. In contrast, as shown in Table 2, Comparatives 61, 67had much lower LCBF of 0.000330 and 0.000400, respectively, and thesesamples were well described by the linear Reference Line shown in FIG. 1(the open triangle symbols), i.e. Comparatives 61 and 67 have not haveLCB, or have an undetectable level of LCB.

Comparative 61 was produced in a solution process pilot plant using anunbridged single site catalyst formulation (Formula (II)) in both thefirst and second reactor, where the reactors were configured in series.Comparative 67 was produced in a commercial-scale solution process usingan unbridged single site catalyst formulation in both the first andsecond reactor, where the reactors were configured in series.

As shown in FIG. 1, the calculation of the LCBF was based on theHorizontal-Shift (S_(h)) and Vertical-Shift (S_(v)) from the linearreference line, as defined by the following equations:S _(h)=Log(ZSV_(c))−4.7619×Log(IV_(c))−3.7519  Eq. (5)S _(v)=0.2100×Log(ZSV_(c))−Log(IV_(c))−0.7879  Eq. (6).

In Eq. (5) and (6), it is required that ZSV_(c) and IV_(c) havedimensions of poise and dL/g, respectively. The Horizontal-Shift (S_(h))was a shift in ZSV_(c) at constant Intrinsic Viscosity (IV_(c)), if oneremoves the Log function its physical meaning is apparent, i.e. a ratioof two Zero Shear Viscosities, the ZSV_(c) of the sample under testrelative to the ZSV_(c) of a linear ethylene polymer having the sameIV_(c). The Horizontal-Shift (S_(h)) was dimensionless. TheVertical-Shift (S_(v)) was a shift in IV_(c) at constant Zero ShearViscosity (ZSV_(c)), if one removes the Log function its physicalmeaning is apparent, i.e. a ratio of two Intrinsic Viscosities, theIV_(c) of a linear ethylene polymer having the same ZSV_(c) relative tothe IV_(c) of the sample under test. The Vertical-Shift (S_(v)) wasdimensionless.

The dimensionless Long Chain Branching Factor (LCBF) was defined byEq.(7):

$\begin{matrix}{{LCBF} = \frac{S_{h} \times S_{v}}{2}} & {{Eq}.\mspace{14mu}(7)}\end{matrix}$

Given the data in Table 2, the LCBF of Examples and Comparatives werecalculated. To be more clear, as shown in Table 2, the S_(h) and S_(v)of Example 51 were 0.593 and 0.124, respectively, thus the LCBF was0.0368 ((0.593×0.124)/2). In contrast, the S_(h) and S_(v) ofComparative 61 were 0.0560 and 0.0118, respectively, thus the LCBF was0.00033 ((0.0560×0.0118)/2).

In this disclosure, resins having no LCB (or undetectable LCB) werecharacterized by a LCBF of less than 0.001 (dimensionless), as evidencedby Table 1B where the reference resins had LCBF values ranging from0.000426 to 1.47×10⁻⁹.

In this disclosure, resins having LCB were characterized by a LCBF of0.001 (dimensionless), as evidenced by Examples 50-52 and Example 58shown in Table 2 that had LCBF that ranged from 0.00845 and 0.0484.

Table 3 summarizes the LCBF of Comparatives A-C and Comparatives D-G.Comparatives A-C (open diamond in FIG. 1) were believed to be producedin a solution process employing one reactor and a constrained geometrysingle site catalyst formulation, i.e. AFFINITY™ PL 1880 (threedifferent samples (lots)). AFFINITY™ products are ethylene/1-octeneinterpolymers available from The Dow Chemical Company (Midland, Mich.,USA). It has been well documented in the art that the constrainedgeometry catalyst produces long chain branched ethylene/1-octenecopolymers, as evidenced by the LCBF values disclosed in Table 3, i.e.from 0.0396 to 0.0423. Comparatives D-G (the open circles in FIG. 1)were believed to be solution process series dual reactor and dualcatalyst ethylene interpolymers, where a constrained geometry singlesite catalyst formulation was employed in a first reactor and a batchZiegler-Natta catalyst formulation was employed in a second reactor,i.e. Elite® 5401G and Elite® 5100G (two different samples (lots)) andElite® 5400G, respectively. Elite® products are ethylene/1-octeneinterpolymers available from The Dow Chemical Company (Midland, Mich.,USA). As shown in Table 3, Comparatives D-G had LCBF values from 0.00803to 0.0130.

¹³C NMR Determination of Long Chain Branching in the First EthyleneInterpolymer

Examples of ethylene interpolymer product, disclosed herein, contain afirst ethylene interpolymer that was produced with a first homogeneouscatalyst formulation. One embodiment of the first homogenous catalystformulation was a bridged metallocene catalyst formulation, thiscatalyst formulation produced a long chain branched (LCB) first ethyleneinterpolymer. Pure samples of the first ethylene interpolymer wereproduced using the Continuous Polymerization Unit (CPU). The CPU wasfully described in the ‘Continuous Polymerization Unit (CPU)’ section ofthis disclosure. The CPU employs one reactor and one catalystformulation was used. The CPU and the bridged metallocene catalystformulation containing Component A [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] wereused to produce examples of the first ethylene interpolymer and theamount of long chain branching in this interpolymer was measured by ¹³CNMR. Table 13x illustrates typical CPU operating continues for thebridged metallocene catalyst formulating to produce a first ethyleneinterpolymer at three reactor temperatures (130° C., 160° C. and 190°C.) and two levels of ethylene conversion, i.e. low ethylene conversion(about 75%) and high ethylene conversion (about 94%). No hydrogen wasused.

Table 14 discloses the amount of LCB in Examples C10 to C15, i.e. puresamples of the first ethylene interpolymer, produced with the bridgedmetallocene catalyst formulation, as determined by ¹³C-NMR (nuclearmagnetic resonance). Examples C10 to C15 were ethylene homopolymersproduced on the CPU at three reactor temperatures (190° C., 160° C. and130° C.), three levels of ethylene conversions, i.e. about 95 wt %,about 85 wt % and about 75 wt % and no hydrogen was used. As shown inTable 14, the amount of long chain branching in the first ethyleneinterpolymer varied from 0.03 LCB/1000 C to 0.23 LCB/1000 C.

Component C

In this disclosure, at least two catalyst formulations were employed tosynthesize embodiments of the ethylene interpolymer products. Onecatalyst formulation was the first homogeneous catalyst formulation; oneembodiment of the first homogeneous catalyst was a bridged metallocenecatalyst formulation containing component A, described above. The othercatalyst formulation was the second homogeneous catalyst formulation;one embodiment of the second homogeneous catalyst formulation was “anunbridged single site catalyst formulation” containing a bulkyligand-metal complex, hereinafter “component C”, represented by Formula(II).(L^(A))_(a)M(PI)_(b)(Q)_(n)  (II)

In Formula (II): (L^(A)) represents a bulky ligand; M represents a metalatom; PI represents a phosphinimine ligand; Q represents a leavinggroup; a is 0 or 1; b is 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of(a+b+n) equals the valance of the metal M. Non-limiting examples of M inFormula (II) include Group 4 metals, titanium, zirconium and hafnium.

Non-limiting examples of the bulky ligand L^(A) in Formula (II) includeunsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Additional non-limitingexamples include, cyclopentaphenanthreneyl ligands, unsubstituted orsubstituted indenyl ligands, benzindenyl ligands, unsubstituted orsubstituted fluorenyl ligands, octahydrofluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In other embodiments,L^(A) may be any other ligand structure capable of q-bonding to themetal M, such embodiments include both η³-bonding and η⁵-bonding to themetal M. In other embodiments, L^(A) may comprise one or moreheteroatoms, for example, nitrogen, silicon, boron, germanium, sulfurand phosphorous, in combination with carbon atoms to form an open,acyclic, or a fused ring, or ring system, for example, aheterocyclopentadienyl ancillary ligand. Other non-limiting embodimentsfor L^(A) include bulky amides, phosphides, alkoxides, aryloxides,imides, carbolides, borollides, porphyrins, phthalocyanines, corrins andother polyazomacrocycles.

The phosphinimine ligand, PI, is defined by Formula (III):(R^(p))₃P═N—  (III)wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

The leaving group Q is any ligand that can be abstracted from Formula(II) forming a catalyst species capable of polymerizing one or moreolefin(s). In some embodiments, Q is a monoanionic labile ligand havinga sigma bond to M. Depending on the oxidation state of the metal, thevalue for n is 1 or 2 such that Formula (II) represents a neutral bulkyligand-metal complex. Non-limiting examples of Q ligands include ahydrogen atom, halogens, C₁₋₂₀ hydrocarbyl radicals, C₁₋₂₀ alkoxyradicals, C₅₋₁₀ aryl oxide radicals; these radicals may be linear,branched or cyclic or further substituted by halogen atoms, C₁₋₁₀ alkylradicals, C₁₋₁₀ alkoxy radicals, C₆₋₁₀ arly or aryloxy radicals. Furthernon-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms. In another embodiment, two Q ligands may formpart of a fused ring or ring system.

Further embodiments of component C include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof ofthe bulky ligand-metal complex shown in Formula (II).

In this disclosure, unique chemical species of component C (Formula(II)) are denoted by the terms “component C1”, “component C2” and“component C3”, etc. While not to be construed as limiting, two speciesof component C were employed as examples in this disclosure.Specifically: “component C1” refers to cyclopentadienyl tri(tertiarybutyl) phosphinimine titanium dichloride having the molecular formula[Cp[(t-Bu)₃PN]TiCl₂] abbreviated “PIC-1” in Table 4A, and; “componentC2” refers to cyclopentadienyl tri(isopropyl)phosphinimine titaniumdichloride having the molecular formula [Cp[(isopropyl)₃PN]TiCl₂]abbreviated “PIC-2” in Table 4A. In this disclosure, component C1 andcomponent C2 were used as the source of bulky ligand-metal complex toprepare two examples of the unbridged single site catalyst formulation.

Comparative Ethylene Interpolymer Products

In this disclosure, Comparative ethylene interpolymer products wereproduced by replacing the first homogeneous catalyst formulation,responsible for producing the first ethylene interpolymer, with a thirdhomogeneous catalyst formulation. One embodiment of the thirdhomogeneous catalyst formulation was an unbridged single site catalystformulation where the bulky ligand-metal complex was a member of thegenus defined by Formula (II), for example component C described above.As shown in Table 4A, Comparative 60 was produced employing PIC-2 inboth reactors 1 and 2, where reactor 1 and 2 were configured in series.Comparative 61 was produced employing PIC-1 in both reactors 1 and 2,where reactor 1 and 2 were configured in parallel. Comparative 67 wasproduced employing an unbridged single site catalyst formulation in bothreactors 1 and 2, where reactor 1 and 2 were configured in parallel. Asshown in Table 2 and FIG. 1, Comparatives 61 and 67 had undetectablelevels of LCB, as evidenced by the dimensionless Long Chain BranchingFactor (LCBF) of less than 0.001, e.g. LCBF ranged from 0.00033 to0.00040, respectively.

Homogeneous Catalyst Formulations

In this disclosure the non-limiting “Examples” of ethylene interpolymerproduct were prepared by employing a bridged metallocene catalystformulation in a first reactor. The bridged metallocene catalystformulation contains a component A (defined above), a component M^(A), acomponent B^(A) and a component P^(A). Components M, B and P are definedbelow and the superscript “^(A)” denotes that fact that the respectivecomponent was part of the catalyst formulation containing component A,i.e. the bridged metallocene catalyst formulation.

In this disclosure “Comparative” ethylene interpolymers were prepared byemploying an unbridged single site catalyst formulation in the firstreactor. In other words, in Comparative samples, the unbridged singlesite catalyst formulation replaced the bridged metallocene catalystformulation in the first reactor. The unbridged single site catalystformulation contains a component C (defined above), a component M^(C), acomponent B^(C) and a component P^(C). Components M, B and P are definedbelow and the superscript “^(C)” denoted that fact that the respectivecomponent was part of the catalyst formulation containing component C,i.e. the unbridged single site catalyst formulation.

The catalyst components M, B and P were independently selected for eachcatalyst formulation. To be more clear: components M^(A) and M^(C) may,or may not be, the same chemical compound; components B^(A) and B^(C)may, or may not be, the same chemical compound, and; components P^(A)and P^(C) may, or may not be, the same chemical compound. Further,catalyst activity was optimized by independently adjusting the moleratios of the components in each catalyst formulation.

Components M, B and P were not particularly limited, i.e. a wide varietyof components can be used as described below.

Component M functioned as a co-catalyst that activated component A orcomponent C, into a cationic complex that effectively polymerizedethylene, or mixtures of ethylene and α-olefins, producing highmolecular weight ethylene interpolymers. In the bridged metallocenecatalyst formulation and the unbridged single site catalyst formulationthe respective component M was independently selected from a variety ofcompounds and those skilled in the art will understand that theembodiments in this disclosure are not limited to the specific chemicalcompound disclosed. Suitable compounds for component M included analumoxane co-catalyst (an equivalent term for alumoxane is aluminoxane).Although the exact structure of an alumoxane co-catalyst was uncertain,subject matter experts generally agree that it was an oligomeric speciesthat contain repeating units of the general Formula (IV):(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂  (IV)where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alumoxane was methylaluminoxane (or MMAO-7) wherein each R group in Formula (IV) is a methylradical.

Component B was an ionic activator. In general, ionic activators arecomprised of a cation and a bulky anion; wherein the latter issubstantially non-coordinating.

In the bridged metallocene catalyst formulation and the unbridged singlesite catalyst formulation the respective component B was independentlyselected from a variety of compounds and those skilled in the art willunderstand that the embodiments in this disclosure are not limited tothe specific chemical compound disclosed. Non-limiting examples ofcomponent B were boron ionic activators that are four coordinate withfour ligands bonded to the boron atom. Non-limiting examples of boronionic activators included the following Formulas (V) and (VI) shownbelow;[R⁵]⁺[B(R⁷)₄]⁻  (V)where B represented a boron atom, R⁵ was an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ was independently selected fromphenyl radicals which were unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich were unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ was independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and; compounds of formula(VI);[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻  (VI)where B was a boron atom, H was a hydrogen atom, Z was a nitrogen orphosphorus atom, t was 2 or 3 and R⁸ was selected from C₁₋₈ alkylradicals, phenyl radicals which were unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ was as defined above inFormula (VI).

In both Formula (V) and (VI), a non-limiting example of R⁷ was apentafluorophenyl radical. In general, boron ionic activators may bedescribed as salts of tetra(perfluorophenyl) boron; non-limitingexamples include anilinium, carbonium, oxonium, phosphonium andsulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl(or triphenylmethylium). Additional non-limiting examples of ionicactivators included: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators included N,N-dimethylaniliniumtetrakispentafluorophenyl borate, and triphenylmethyliumtetrakispentafluorophenyl borate.

Component P is a hindered phenol and is an optional component in therespective catalyst formulation. In the bridged metallocene catalystformulation and the unbridged single site catalyst formulation therespective component P was independently selected from a variety ofcompounds and those skilled in the art will understand that theembodiments in this disclosure are not limited to the specific chemicalcompound disclosed. Non-limiting example of hindered phenols includedbutylated phenolic antioxidants, butylated hydroxytoluene,2,4-di-tertiarybutyl-6-ethyl phenol, 4,4′-methylenebis(2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

As fully described below, a highly active first homogeneous catalystformulation, or in one specific embodiment a highly active bridgedmetallocene catalyst formulation was produced by optimizing the quantityand mole ratios of the four components in the formulation; for example,component A1, component M^(A1), component B^(A1) and component P^(A1).Where highly active means a very large amount of ethylene interpolymeris produced from a very small amount of catalyst formulation. Similarly,a highly active third homogeneous catalyst formulation or an unbridgedsingle site catalyst formulation (comparative catalyst formulations)were produced by optimizing the quantity and mole ratios of the fourcomponents in the formulation; e.g., one embodiment comprises acomponent C1, a component M^(C1), a component B^(C1) and a componentP^(C1).

Heterogeneous Catalyst Formulations

A number of heterogeneous catalyst formulations are well known to thoseskilled in the art, including, as non-limiting examples, Ziegler-Nattaand chromium catalyst formulations. In this disclosure, optionally aheterogeneous catalyst formulation may be employed to synthesize thethird ethylene interpolymer in a third reactor. The catalytic metal inthe heterogeneous catalyst formulation was identified by the term “metalZ”.

In this disclosure, embodiments were described where the heterogeneouscatalyst formulation was “an in-line Ziegler-Natta catalyst formulation”or “a batch Ziegler-Natta catalyst formation”. The term “in-line”referred to the continuous synthesis of a small quantity of activeZiegler-Natta catalyst and immediately injecting this catalyst into thethird reactor, wherein ethylene and one or more optional α-olefins werepolymerized to form the optional third ethylene interpolymer. The term“batch” referred to the synthesis of a much larger quantity of catalystor procatalyst in one or more mixing vessels that were external to, orisolated from, the continuously operating solution polymerizationprocess. Once prepared, the batch Ziegler-Natta catalyst formulation, orbatch Ziegler-Natta procatalyst, was transferred to a catalyst storagetank. The term “procatalyst” referred to an inactive catalystformulation (inactive with respect to ethylene polymerization); theprocatalyst was converted into an active catalyst by adding an alkylaluminum co-catalyst. As needed, the procatalyst was pumped from thestorage tank to at least one continuously operating reactor, wherein anactive catalyst polymerizes ethylene and one or more optional α-olefinsto form an ethylene interpolymer. The procatalyst may be converted intoan active catalyst in the reactor or external to the reactor.

A wide variety of chemical compounds can be used to synthesize an activeZiegler-Natta catalyst formulation. The following describes variouschemical compounds that may be combined to produce an activeZiegler-Natta catalyst formulation. Those skilled in the art willunderstand that the embodiments in this disclosure are not limited tothe specific chemical compound disclosed.

An active Ziegler-Natta catalyst formulation may be formed from: amagnesium compound, a chloride compound, a metal compound, an alkylaluminum co-catalyst and an aluminum alkyl. In this disclosure, the term“component (v)” is equivalent to the magnesium compound, the term“component (vi)” is equivalent to the chloride compound, the term“component (vii)” is equivalent to the metal compound, the term“component (viii)” is equivalent to the alkyl aluminum co-catalyst andthe term “component (ix)” is equivalent to the aluminum alkyl. As willbe appreciated by those skilled in the art, Ziegler-Natta catalystformulations may contain additional components; a non-limiting exampleof an additional component is an electron donor, e.g. amines or ethers.

A non-limiting example of an active in-line Ziegler-Natta catalystformulation can be prepared as follows. In the first step, a solution ofa magnesium compound (component (v)) is reacted with a solution of thechloride compound (component (vi)) to form a magnesium chloride supportsuspended in solution. Non-limiting examples of magnesium compoundsinclude Mg(R¹)₂; wherein the R¹ groups may be the same or different,linear, branched or cyclic hydrocarbyl radicals containing 1 to 10carbon atoms. Non-limiting examples of chloride compounds include R²Cl;wherein R² represents a hydrogen atom, or a linear, branched or cyclichydrocarbyl radical containing 1 to 10 carbon atoms. In the first step,the solution of magnesium compound may also contain an aluminum alkyl(component (ix)). Non-limiting examples of aluminum alkyl includeAl(R³)₃, wherein the R³ groups may be the same or different, linear,branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbonatoms. In the second step a solution of the metal compound (component(vii)) is added to the solution of magnesium chloride and the metalcompound is supported on the magnesium chloride. Non-limiting examplesof suitable metal compounds include M(X)_(n) or MO(X)_(n); where Mrepresents a metal selected from Group 4 through Group 8 of the PeriodicTable, or mixtures of metals selected from Group 4 through Group 8; Orepresents oxygen, and; X represents chloride or bromide; n is aninteger from 3 to 6 that satisfies the oxidation state of the metal.Additional non-limiting examples of suitable metal compounds includeGroup 4 to Group 8 metal alkyls, metal alkoxides (which may be preparedby reacting a metal alkyl with an alcohol) and mixed-ligand metalcompounds that contain a mixture of halide, alkyl and alkoxide ligands.In the third step a solution of an alkyl aluminum co-catalyst (component(viii)) is added to the metal compound supported on the magnesiumchloride. A wide variety of alkyl aluminum co-catalysts are suitable, asexpressed by Formula (VII):Al(R⁴)_(p)(OR⁵)_(q)(X)_(r)  (VII)wherein the R⁴ groups may be the same or different, hydrocarbyl groupshaving from 1 to 10 carbon atoms; the OR⁵ groups may be the same ordifferent, alkoxy or aryloxy groups wherein R⁵ is a hydrocarbyl grouphaving from 1 to 10 carbon atoms bonded to oxygen; X is chloride orbromide, and; (p+q+r)=3, with the proviso that p is greater than 0.Non-limiting examples of commonly used alkyl aluminum co-catalystsinclude trimethyl aluminum, triethyl aluminum, tributyl aluminum,dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminumbutoxide, dimethyl aluminum chloride or bromide, diethyl aluminumchloride or bromide, dibutyl aluminum chloride or bromide and ethylaluminum dichloride or dibromide.

The process described in the paragraph above, to synthesize an activein-line Ziegler-Natta catalyst formulation, can be carried out in avariety of solvents; non-limiting examples of solvents include linear orbranched C₅ to C₁₂ alkanes or mixtures thereof.

To produce an active in-line Ziegler-Natta catalyst formulation thequantity and mole ratios of the five components, (v) through (ix), areoptimized as described below.

Additional embodiments of heterogeneous catalyst formulations includeformulations where the “metal compound” is a chromium compound;non-limiting examples include silyl chromate, chromium oxide andchromocene. In some embodiments, the chromium compound is supported on ametal oxide such as silica or alumina. Heterogeneous catalystformulations containing chromium may also include co-catalysts;non-limiting examples of co-catalysts include trialkylaluminum,alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.

Solution Polymerization Process

The disclosed continuous solution polymerization process is improved byhaving one or more of: 1) at least a 70% reduced [α-olefin/ethylene]weight ratio as defined by the following formula,

${\%\mspace{14mu}{{Reduced}\left\lbrack \frac{\alpha\text{-}{olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight ofthe α-olefin added to the first reactor by the weight of ethylene addedto the first reactor, wherein a first ethylene interpolymer is producedhaving “a target density” using a first homogeneous catalystformulation, and; (α-olefin/ethylene)^(C) is calculated by dividing theweight of the α-olefin added to the first reactor by the weight of theethylene added to the first reactor, wherein a control ethyleneinterpolymer having the target density is produced by replacing thefirst homogeneous catalyst formulation with a third homogeneous catalystformulation, and/or; 2) the first ethylene interpolymer at least a 5%improved weight average molecular weight as defined by the followingformula% Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5%wherein M_(w) ^(A) is a weight average molecular weight of the firstethylene interpolymer and M_(w) ^(C) is a weight average molecularweight of a comparative ethylene interpolymer; wherein said comparativeethylene interpolymer is produced in the first reactor by replacing thefirst homogeneous catalyst formulation with the third homogeneouscatalyst formulation.

Embodiments of the improved continuous solution polymerization processare shown in FIG. 2. FIG. 2 is not to be construed as limiting, it beingunderstood, that embodiments are not limited to the precise arrangementof, or the number of, vessels shown.

In an embodiment of the continuous solution polymerization process,process solvent, monomer(s) and a catalyst formulation are continuouslyfed to a reactor wherein the desired ethylene interpolymer is formed insolution. In FIG. 2, process solvent 1, ethylene 2 and optional α-olefin3 are combined to produce reactor feed stream RF1 which flows intoreactor 11 a. In FIG. 2 optional streams, or optional embodiments, aredenoted with dotted lines. It is not particularly important thatcombined reactor feed stream RF1 be formed; i.e. reactor feed streamscan be combined in all possible combinations, including an embodimentwhere streams 1 through 3 are independently injected into reactor 11 a.Optionally hydrogen may be injected into reactor 11 a through stream 4;hydrogen may be added to control (reduce) the molecular weight of thefirst ethylene interpolymer produced in reactor 11 a. Reactor 11 a iscontinuously stirred by stirring assembly 11 b which includes a motorexternal to the reactor and an agitator within the reactor. In the art,such a reactor is frequently called a CSTR (Continuously Stirred TankReactor).

A first homogeneous catalyst formulation is injected into reactor 11 athrough stream 5 e. An embodiment of the first homogeneous catalystformulation is a bridged metallocene catalyst formulation. The bridgedmetallocene catalyst formulation (described above) was employed inreactor 11 a to produce all of the Examples in this disclosure. Incontrast, a third homogeneous catalyst formulation was employed inreactor 11 a to produce all of the Comparatives in this disclosure. Asdescribed above, one embodiment of the third homogeneous catalystformulation was an unbridged single site catalyst formulation.

Referring to FIG. 2, the bridged metallocene catalyst formulation wasprepared by combining: stream 5 a, containing a component P^(A1)dissolved in a catalyst component solvent; stream 5 b, containing acomponent M^(A1) dissolved in a catalyst component solvent; stream 5 c,containing a bulky ligand-metal complex component A1 dissolved in acatalyst component solvent, and; stream 5 d, containing component B^(A1)dissolved in a catalyst component solvent. The bridged metallocenecatalyst formulation was then injected into reactor 11 a via processstream 5 e. Any combination of the streams employed to prepare anddeliver the bridged metallocene catalyst formulation may be heated orcooled, i.e. streams 5 a through 5 e.

The “R1 catalyst inlet temperature”, defined as the temperature of thesolution containing the bridged metallocene catalyst formulation (stream5 e) prior to injection into reactor 11 a, was controlled. In some casesthe upper temperature limit on the R1 catalyst inlet temperature may beabout 180° C., in other cases about 160° C. and in still other casesabout 150° C., and; in some cases the lower temperature limit on the R1catalyst inlet temperature may be about 80° C., in other cases 100° C.and in still other cases about 120° C. In still other cases the uppertemperature limit on the R1 catalyst inlet temperature may be about 70°C., in other cases about 60° C. and in still other cases about 50° C.,and; in some cases the lower temperature limit on the R1 catalyst inlettemperature may be about 0° C., in other cases 10° C. and in still othercases about 20° C.

Each catalyst component was dissolved in a catalyst component solvent.The catalyst component solvent used for each catalyst component may bethe same or different. Catalyst component solvents are selected suchthat the combination of catalyst components does not produce aprecipitate in any process stream; for example, precipitation of acatalyst components in stream 5 e. The optimization of the catalystformulations are described below.

Reactor 11 a produces a first exit stream, stream 11 c, containing thefirst ethylene interpolymer dissolved in process solvent, as well asunreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen(if present), active first homogeneous catalyst, deactivated catalyst,residual catalyst components and other impurities (if present). Meltindex ranges and density ranges of the first ethylene interpolymerproduced are described below.

The continuous solution polymerization process shown in FIG. 2 includestwo embodiments where reactors 11 a and 12 a can be operated in seriesor parallel modes. In series mode 100% of stream 11 c (the first exitstream) passes through flow controller 11 d forming stream 11 e whichenters reactor 12 a. In contrast, in parallel mode 100% of stream 11 cpasses through flow controller 11 f forming stream 11 g. Stream 11 gby-passes reactor 12 a and is combined with stream 12 c (the second exitstream) forming stream 12 d (the third exit stream).

Fresh reactor feed streams are injected into reactor 12 a; processsolvent 6, ethylene 7 and optional α-olefin 8 are combined to producereactor feed stream RF2. It is not important that stream RF2 is formed;i.e. reactor feed streams can be combined in all possible combinations,including independently injecting each stream into the reactor.Optionally hydrogen may be injected into reactor 12 a through stream 9to control (reduce) the molecular weight of the second ethyleneinterpolymer. Reactor 12 a is continuously stirred by stirring assembly12 b which includes a motor external to the reactor and an agitatorwithin the reactor.

A second homogeneous catalyst formulation was injected in reactor 12 athrough stream 10 e, one embodiment of the second homogeneous catalystformulation is an unbridged single site catalyst formulation whichproduces a second ethylene interpolymer in reactor 12 a. The componentsthat comprise the unbridged single site catalyst formulation areintroduced through streams 10 a, 10 b, 10 c and 10 d. The unbridgedsingle site catalyst formulation was prepared by combining: stream 10 a,containing a component P^(C1) dissolved in a catalyst component solvent;stream 10 b, containing a component M^(C1) dissolved in a catalystcomponent solvent; stream 10 c, containing a bulky ligand-metal complexcomponent C1 dissolved in a catalyst component solvent, and; stream 10d, containing component B^(C1) dissolved in a catalyst componentsolvent. The unbridged single site catalyst formulation was theninjected into reactor 12 a via process stream 10 e. Any combination ofthe streams employed to prepare and deliver the unbridged single sitecatalyst formulation may be heated or cooled, i.e. streams 10 a through10 e. Each catalyst component was dissolved in a catalyst componentsolvent. The catalyst component solvents used to synthesize theunbridged single site catalyst formulation may be the same or different.Catalyst component solvents are selected such that the combination ofcatalyst components does not produce a precipitate in any processstream; for example, precipitation of a catalyst components in stream 10e. The optimization of the catalyst formulations are described below.The “R2 catalyst inlet temperature”, defined as the temperature of thesolution containing the bridged metallocene catalyst formulation (stream10 e) prior to injection into reactor 12 a, was controlled. In somecases the upper temperature limit on the R2 catalyst inlet temperaturemay be about 70° C., in other cases about 60° C. and in still othercases about 50° C., and; in some cases the lower temperature limit onthe R2 catalyst inlet temperature may be about 0° C., in other cases 10°C. and in still other cases about 20° C. Any combination of the streamsemployed to prepare and deliver the second homogeneous catalystformulation to the second reactor (R2) may be heated or cooled, i.e.streams 10 a through 10 e.

Injection of the second homogeneous catalyst formulation into reactor 12a produces a second ethylene interpolymer and a second exit stream 12 c.

If reactors 11 a and 12 a are operated in a series mode, the second exitstream 12 c contains the second ethylene interpolymer and the firstethylene interpolymer dissolved in process solvent; as well as unreactedethylene, unreacted α-olefins (if present), unreacted hydrogen (ifpresent), active catalysts, deactivated catalysts, catalyst componentsand other impurities (if present). Optionally the second exit stream 12c is deactivated by adding a catalyst deactivator A from catalystdeactivator tank 18A forming a deactivated solution A, stream 12 e; inthis case, FIG. 2 defaults to a dual reactor solution process. If thesecond exit stream 12 c is not deactivated the second exit stream enterstubular reactor 17. Catalyst deactivator A is discussed below.

If reactors 11 a and 12 a are operated in parallel mode, the second exitstream 12 c contains the second ethylene interpolymer dissolved inprocess solvent. The second exit stream 12 c is combined with stream 11g forming a third exit stream 12 d, the latter contains the secondethylene interpolymer and the first ethylene interpolymer dissolved inprocess solvent; as well as unreacted ethylene, unreacted α-olefins (ifpresent), unreacted hydrogen (if present), active catalyst, deactivatedcatalyst, catalyst components and other impurities (if present).Optionally the third exit stream 12 d is deactivated by adding catalystdeactivator A from catalyst deactivator tank 18A forming deactivatedsolution A, stream 12 e; in this case, FIG. 2 defaults to a dual reactorsolution process. If the third exit stream 12 d is not deactivated thethird exit stream 12 d enters tubular reactor 17.

The term “tubular reactor” is meant to convey its conventional meaning,namely a simple tube; wherein the length/diameter (L/D) ratio is atleast 10/1. Optionally, one or more of the following reactor feedstreams may be injected into tubular reactor 17; process solvent 13,ethylene 14 and α-olefin 15. As shown in FIG. 2, streams 13, 14 and 15may be combined forming reactor feed stream RF3 and the latter isinjected into reactor 17. It is not particularly important that streamRF3 be formed; i.e. reactor feed streams can be combined in all possiblecombinations. Optionally hydrogen may be injected into reactor 17through stream 16.

Optionally, the first and/or the second homogeneous catalystformulations may be injected into reactor 17 (not shown in FIG. 2). Thiscould be accomplished by feeding a portion of stream 5 e to reactor 17and/or feeding a portion of stream 10 e to reactor 17. Alternatively, anon-limiting embodiment includes a fifth homogenous catalyst assembly(not shown in FIG. 2) that manufactures and injects a fifth homogeneouscatalyst formulation into reactor 17. The fifth homogeneous catalystassembly refers to a combination of tanks, conduits and flow controllerssimilar to 5 a through 5 e shown in FIG. 2 (i.e. the first homogeneouscatalyst assembly) or similar to 10 a through 10 e shown in FIG. 2 (i.e.the second homogeneous catalyst assembly). The fifth homogeneouscatalyst formulation may be the first homogeneous catalyst formulation,the second homogeneous catalyst formulation or the fourth homogeneouscatalyst formulation.

Optionally, a heterogeneous catalyst formulation may be injected intoreactor 17. One embodiment of a heterogeneous catalyst formulationincludes an in-line Ziegler-Natta catalyst formulation. FIG. 2illustrates an in-line heterogeneous catalyst assembly, defined byconduits and flow controllers 34 a through 34 h, that manufactures andinjects an in-line Ziegler-Natta catalyst formulation into tubularreactor 17.

The in-line heterogeneous catalyst assembly generates a high activitycatalyst by optimizing hold-up-times and the following molar ratios:(aluminum alkyl)/(magnesium compound), (chloride compound)/(magnesiumcompound), (alkyl aluminum co-catalyst/(metal compound, and (aluminumalkyl)/(metal compound). To be clear: stream 34 a contains a binaryblend of magnesium compound (component (v)) and aluminum alkyl(component (ix)) in process solvent; stream 34 b contains a chloridecompound (component (vi)) in process solvent; stream 34 c contains ametal compound (component (vii)) in process solvent, and; stream 34 dcontains an alkyl aluminum co-catalyst (component (viii)) in processsolvent. To produce a highly active in-line Ziegler-Natta catalyst(highly active in olefin polymerization), the (chloridecompound)/(magnesium compound) molar ratio is optimized. The upper limiton the (chloride compound)/(magnesium compound) molar ratio may be about4, in some cases about 3.5 and is other cases about 3.0. The lower limiton the (chloride compound)/(magnesium compound) molar ratio may be about1.0, in some cases about 1.5 and in other cases about 1.9. The timebetween the addition of the chloride compound and the addition of themetal compound (component (vii)) via stream 34 c is controlled;hereinafter HUT-1 (the first Hold-Up-Time). HUT-1 is the time forstreams 34 a and 34 b to equilibrate and form a magnesium chloridesupport. The upper limit on HUT-1 may be about 70 seconds, in some casesabout 60 seconds and is other cases about 50 seconds. The lower limit onHUT-1 may be about 5 seconds, in some cases about 10 seconds and inother cases about 20 seconds. HUT-1 is controlled by adjusting thelength of the conduit between stream 34 b injection port and stream 34 cinjection port, as well as controlling the flow rates of streams 34 aand 34 b. The time between the addition of component (vii) and theaddition of the alkyl aluminum co-catalyst, component (viii), via stream34 d is controlled; hereinafter HUT-2 (the second Hold-Up-Time). HUT-2is the time for the magnesium chloride support and stream 34 c to reactand equilibrate. The upper limit on HUT-2 may be about 50 seconds, insome cases about 35 seconds and is other cases about 25 seconds. Thelower limit on HUT-2 may be about 2 seconds, in some cases about 6seconds and in other cases about 10 seconds. HUT-2 is controlled byadjusting the length of the conduit between stream 34 c injection portand stream 34 d injection port, as well as controlling the flow rates ofstreams 34 a, 34 b and 34 c. The quantity of the alkyl aluminumco-catalyst added is optimized to produce an efficient catalyst; this isaccomplished by adjusting the (alkyl aluminum co-catalyst)/(metalcompound) molar ratio, or (viii)/(vii) molar ratio. The upper limit onthe (alkyl aluminum co-catalyst)/(metal compound) molar ratio may beabout 10, in some cases about 7.5 and is other cases about 6.0. Thelower limit on the (alkyl aluminum co-catalyst)/(metal compound) molarratio may be 0, in some cases about 1.0 and in other cases about 2.0. Inaddition, the time between the addition of the alkyl aluminumco-catalyst and the injection of the in-line Ziegler-Natta catalystformulation into reactor 17 is controlled; hereinafter HUT-3 (the thirdHold-Up-Time). HUT-3 is the time for stream 34 d to intermix andequilibrate to form the in-line Ziegler Natta catalyst formulation. Theupper limit on HUT-3 may be about 15 seconds, in some cases about 10seconds and is other cases about 8 seconds. The lower limit on HUT-3 maybe about 0.5 seconds, in some cases about 1 seconds and in other casesabout 2 seconds. HUT-3 is controlled by adjusting the length of theconduit between stream 34 d injection port and the catalyst injectionport in reactor 17, and by controlling the flow rates of streams 34 athrough 34 d. As shown in FIG. 2, optionally, 100% of stream 34 d, thealkyl aluminum co-catalyst, may be injected directly into reactor 17 viastream 34 h. Optionally, a portion of stream 34 d may be injecteddirectly into reactor 17 via stream 34 h and the remaining portion ofstream 34 d injected into reactor 17 via stream 34 f. In FIG. 2, thein-line heterogeneous catalyst assembly supplies 100% of the catalyst toreactor 17. Any combination of the streams that comprise the in-lineheterogeneous catalyst assembly may be heated or cooled, i.e. streams 34a-34 e and 34 h; in some cases the upper temperature limit of streams 34a-34 e and 34 h may be about 90° C., in other cases about 80° C. and instill other cases about 70° C. and; in some cases the lower temperaturelimit may be about 20° C.; in other cases about 35° C. and in stillother cases about 50° C. The quantity of the in-line Ziegler-Nattacatalyst formulation added to reactor 17 was expressed as theparts-per-million (ppm) of metal compound (component (vii)) in thereactor solution. The upper limit on component (vii) in reactor 17 maybe about 10 ppm, in some cases about 8 ppm and in other cases about 6ppm; while the lower limit may be about 0.5 ppm, in other cases about 1ppm and in still other cases about 2 ppm. The (aluminum alkyl)/(metalcompound) molar ratio in reactor 17, or the (ix)/(vii) molar ratio, isalso controlled. The upper limit on the (aluminum alkyl)/(metalcompound) molar ratio in the reactor may be about 2, in some cases about1.5 and is other cases about 1.0. The lower limit on the (aluminumalkyl)/(metal compound) molar ratio may be about 0.05, in some casesabout 0.075 and in other cases about 0.1.

Optionally, an additional embodiment of a heterogeneous catalystformulation includes a batch Ziegler-Natta catalyst formulation. FIG. 2illustrates a batch heterogeneous catalyst assembly, defined by conduitsand flow controllers 90 a through 90 f. The batch heterogeneous catalystassembly manufactures and injects the batch Ziegler-Natta catalystformulation, or a batch Ziegler-Natta procatalyst, into tubular reactor17.

Processes to prepare batch Ziegler-Natta procatalysts are well known tothose skilled in the art. A non-limiting formulation useful in thedisclosed polymerization process may be prepared as follows. A batchZiegler-Natta procatalyst may be prepared by sequentially added thefollowing components to a stirred mixing vessel: (a) a solution of amagnesium compound (an equivalent term for the magnesium compound is“component (v)”); (b) a solution of a chloride compound (an equivalentterm for the chloride compound is “component (vi)”; (c) optionally asolution of an aluminum alkyl halide, and; (d) a solution of a metalcompound (an equivalent term for the metal compound is “component(vii)”). Suitable, non-limiting examples of aluminum alkyl halides aredefined by the formula (R⁶)_(v)AIX_(3-v); wherein the R⁶ groups may bethe same or different hydrocarbyl group having from 1 to 10 carbonatoms, X represents chloride or bromide, and; v is 1 or 2. Suitable,non-limiting examples of the magnesium compound, the chloride compoundand the metal compound were described earlier in this disclosure.Suitable solvents within which to prepare the procatalyst include linearor branched C₅ to C₁₂ alkanes or mixtures thereof. Individual mixingtimes and mixing temperatures may be used in each of steps (a) through(d). The upper limit on mixing temperatures for steps (a) through (d) insome case may be 160° C., in other cases 130° C. and in still othercases 100° C. The lower limit on mixing temperatures for steps (a)through (d) in some cases may be 10° C., in other cases 20° C. and instill other cases 30° C. The upper limit on mixing time for steps (a)through (d) in some case may be 6 hours, in other cases 3 hours and instill other cases 1 hour. The lower limit on mixing times for steps (a)through (d) in some cases may be 1 minute, in other cases 10 minutes andin still other cases 30 minutes. Batch Ziegler-Natta procatalyst mayhave various catalyst component mole ratios. The upper limit on the(chloride compound)/(magnesium compound) molar ratio in some cases maybe about 3, in other cases about 2.7 and is still other cases about 2.5;the lower limit in some cases may be about 2.0, in other cases about 2.1and in still other cases about 2.2. The upper limit on the (magnesiumcompound)/(metal compound) molar ratio in some cases may be about 10, inother cases about 9 and in still other cases about 8; the lower limit insome cases may be about 5, in other cases about 6 and in still othercases about 7. The upper limit on the (aluminum alkyl halide)/(magnesiumcompound) molar ratio in some cases may be about 0.5, in other casesabout 0.4 and in still other cases about 0.3; the lower limit in somecases may be 0, in other cases about 0.1 and in still other cases about0.2. An active batch Ziegler-Natta catalyst formulation is formed whenthe procatalyst is combined with an alkyl aluminum co-catalyst. Suitableco-catalysts were described earlier in this disclosure. The procatalystmay be activated external to the reactor or in the reactor; in thelatter case, the procatalyst and an appropriate amount of alkyl aluminumco-catalyst are independently injected R2 and optionally R3.

Once prepared the batch Ziegler-Natta procatalyst is pumped toprocatalyst storage tank 90 a shown in FIG. 2. Tank 90 a may, or maynot, be agitated. Storage tank 90 c contains an alkyl,aluminumco-catalyst. A batch Ziegler Natta catalyst formulation stream 90 e,that is efficient in converting olefins to polyolefins, is formed bycombining the batch Ziegler Natta procatalyst stream 90 b with alkylaluminum co-catalyst stream 90 d. Stream 90 e is optionally injectedinto reactor 17, wherein an optional third ethylene interpolymer may beformed. FIG. 2 includes additional embodiments where: (a) the batchZiegler-Natta procatalyst is injected directly into reactor 17 throughstream 90 e and the procatalyst is activated inside reactor 17 byinjecting 100% of the aluminum co-catalyst directly into reactor 17 viastream 90 f, or; (b) a portion of the aluminum co-catalyst may flowthrough stream 90 e with the remaining portion flowing through stream 90f. Any combination of tanks or streams 90 a through 90 f may be heatedor cooled. The time between the addition of the alkyl aluminumco-catalyst and the injection of the batch Ziegler-Natta catalystformulation into reactor 17 is controlled. Referring to FIG. 2, HUT-4 isthe time for stream 90 d to intermix and equilibrate with stream 90 b(batch Ziegler-Natta procatalyst) to form the batch Ziegler Nattacatalyst formulation prior to injection into reactor 17 via in stream 90e. The upper limit on HUT-4 may be about 300 seconds, in some casesabout 200 seconds and in other cases about 100 seconds. The lower limiton HUT-4 may be about 0.1 seconds, in some cases about 1 seconds and inother cases about 10 seconds. The quantity of batch Ziegler-Nattaprocatalyst or batch Ziegler-Natta catalyst formulation added to reactor17 was expressed the parts-per-million (ppm) of metal compound(component (vii)) in the reactor solution. The upper limit on component(vii) may be about 10 ppm, in some cases about 8 ppm and in other casesabout 6 ppm; while the lower limit may be about 0.5 ppm, in some casesabout 1 ppm and in other cases about 2 ppm. The quantity of the alkylaluminum co-catalyst added to reactor 17 is optimized to produce anefficient catalyst; this is accomplished by adjusting the (alkylaluminum co-catalyst)/(metal compound) molar ratio. The upper limit onthe (alkyl aluminum co-catalyst)/(metal compound) molar ratio may beabout 10, in some cases about 8.0 and is other cases about 6.0. Thelower limit on the (alkyl aluminum co-catalyst)/(metal compound) molarratio may be 0.5, in some cases about 0.75 and in other cases about 1.

The quantity of batch Ziegler-Natta procatalyst produced and/or the sizeto procatalyst storage tank 90 a is not particularly important withrespect to this disclosure. However, the large quantity of procatalystproduced allows one to operate the continuous solution polymerizationplant for an extended period of time: the upper limit on this time insome cases may be about 3 months, in other cases for about 2 months andin still other cases for about 1 month; the lower limit on this time insome cases may be about 1 day, in other cases about 1 week and in stillother cases about 2 weeks.

In reactor 17 a third ethylene interpolymer may, or may not, form. Athird ethylene interpolymer will not form if catalyst deactivator A isadded upstream of reactor 17 via catalyst deactivator tank 18A (as shownin FIG. 2). In contrast, A third ethylene interpolymer will be formed ifcatalyst deactivator B is added downstream of reactor 17 via catalystdeactivator tank 18B.

The optional third ethylene interpolymer produced in reactor 17 may beformed using a variety of operational modes; with the proviso thatcatalyst deactivator A is not added upstream of reactor 17. Non-limitingexamples of operational modes include: (a) residual ethylene, residualoptional α-olefin and residual active catalyst entering reactor 17 reactto form the optional third ethylene interpolymer, or; (b) fresh processsolvent 13, fresh ethylene 14 and optionally fresh α-olefin 15 are addedto reactor 17 and the residual active catalyst entering reactor 17 formsthe optional third ethylene interpolymer, or; (c) a fifth homogeneouscatalyst formulation is added to reactor 17 to polymerize residualethylene and residual optional α-olefin to form the third ethyleneinterpolymer, or; (d) an in-line Ziegler-Natta catalyst formulation isadded to reactor 17 via stream 34 e (FIG. 2) to polymerize residualethylene and residual optional α-olefin to form the third ethyleneinterpolymer, or; (e) a batch Ziegler-Natta catalyst formulation isadded to reactor 17 via stream 90 e (FIG. 2) to polymerize residualethylene and residual optional α-olefin to form the third ethyleneinterpolymer, or; (d) fresh process solvent (stream 13), ethylene(stream 14), optional α-olefin (stream 15) and a fifth homogeneouscatalyst formulation, or an in-line Ziegler-Natta catalyst formulationor a batch Ziegler-Natta catalyst formulation are added to reactor 17 toform the third ethylene interpolymer. Optionally fresh hydrogen (stream16) may be added to control (reduce) the molecular weight of the thirdoptional ethylene interpolymer.

In series mode, Reactor 17 produces a third exit stream 17 b containingthe first ethylene interpolymer, the second ethylene interpolymer andoptionally a third ethylene interpolymer. As shown in FIG. 2, catalystdeactivator B may be added to the third exit stream 17 b via catalystdeactivator tank 18B producing a deactivated solution B, stream 19; withthe proviso that catalyst deactivator B is not added if catalystdeactivator A was added upstream of reactor 17. Deactivated solution Bmay also contain unreacted ethylene, unreacted optional α-olefin,unreacted optional hydrogen and impurities if present. As indicatedabove, if catalyst deactivator A was added, deactivated solution A(stream 12 e) exits tubular reactor 17 as shown in FIG. 2.

In parallel mode operation, reactor 17 produces a fourth exit stream 17b containing the first ethylene interpolymer, the second ethyleneinterpolymer and optionally a third ethylene interpolymer. As describedabove, in parallel mode stream 12 d was the third exit stream. As shownin FIG. 2, in parallel mode catalyst deactivator B is added to thefourth exit stream 17 b via catalyst deactivator tank 18B producing adeactivated solution B, stream 19; with the proviso that catalystdeactivator B is not added if catalyst deactivator A was added upstreamof reactor 17.

In FIG. 2, deactivated solution A (stream 12 e) or B (stream 19) passesthrough pressure let down device 20, heat exchanger 21 and optionally apassivator was added via tank 22 forming a passivated solution stream23; the passivator is described below. The passivator was added, andstream 23 was formed, only if a heterogeneous catalyst formulation wasadded to reactor 17. Stream 19, or optional stream 23, passes throughpressure let down device 24 and entered a first vapor/liquid separator25. Hereinafter, “V/L” is equivalent to vapor/liquid. Two streams wereformed in the first V/L separator: a first bottom stream 27 comprising asolution that was rich in ethylene interpolymers and also containsresidual ethylene, residual optional α-olefins and catalyst residues,and; a first gaseous overhead stream 26 comprising ethylene, processsolvent, optional α-olefins, optional hydrogen, oligomers and light-endimpurities if present.

The first bottom stream entered a second V/L separator 28. In the secondV/L separator two streams were formed: a second bottom stream 30comprising a solution that was richer in ethylene interpolymer andleaner in process solvent relative to the first bottom stream 27, and; asecond gaseous overhead stream 29 comprising process solvent, optionalα-olefins, ethylene, oligomers and light-end impurities if present.

The second bottom stream 30 flowed into a third V/L separator 31. In thethird V/L separator two streams were formed: a product stream 33comprising an ethylene interpolymer product, deactivated catalystresidues and less than 5 weight % of residual process solvent, and; athird gaseous overhead stream 32 comprised essentially of processsolvent, optional α-olefins and light-end impurities if present.

Product stream 33 proceeded to polymer recovery operations. Non-limitingexamples of polymer recovery operations include one or more gear pump,single screw extruder or twin screw extruder that forces the moltenethylene interpolymer product through a pelletizer. A devolatilizingextruder may be used to remove small amounts of residual process solventand optional α-olefin, if present. Once pelletized the solidifiedethylene interpolymer product is typically dried and transported to aproduct silo.

The first, second and third gaseous overhead streams shown in FIG. 2(streams 26, 29 and 32, respectively) were sent to a distillation columnwhere solvent, ethylene and optional α-olefin were separated forrecycling, or; the first, second and third gaseous overhead streams wererecycled to the reactors, or; a portion of the first, second and thirdgaseous overhead streams were recycled to the reactors and the remainingportion was sent to a distillation column.

Comparatives

In this disclosure Comparative ethylene interpolymer samples wereproduced by replacing the first homogeneous catalyst formulation (usedin the first reactor (R1)) with a third homogeneous catalystformulation. One embodiment of the first homogeneous catalystformulation was a bridged metallocene catalyst formulation containingcomponent A (represented by Formula (I)) and one embodiment of the thirdhomogeneous catalyst formulation was an unbridged single site catalystformulation containing component C (represented by Formula (II)), asfully described above.

To be more clear, referring to FIG. 2, the third homogeneous catalystformulation or the unbridged single site catalyst formulation wasprepared by combining: stream 5 a, containing component P dissolved in acatalyst component solvent; stream 5 b, containing component M dissolvedin a catalyst component solvent; stream 5 c, containing component Cdissolved in a catalyst component solvent, and; stream 5 d, containingcomponent B dissolved in a catalyst component solvent. The thirdhomogeneous catalyst formulation was then injected into reactor 11 a viaprocess stream 5 e producing a comparative first ethylene interpolymerin reactor 11 a. The “R1 catalyst inlet temperature” was controlled. Inthe case of the unbridged singe site catalyst formulation the uppertemperature limit on the R1 catalyst inlet temperature may be about 70°C., in other cases about 60° C. and in still other cases about 50° C.,and; in some cases the lower temperature limit on the R1 catalyst inlettemperature may be about 0° C., in other cases about 10° C. and in stillother cases about 20° C. The same catalyst component solvents were usedto prepare both the first and third homogeneous catalyst formulations.

For all Comparative ethylene interpolymer products disclosed, the secondhomogeneous catalyst formulation (described above) was injected intoreactor 12 a (R2), wherein the second ethylene interpolymer was formed.Comparative ethylene interpolymer products were an in-situ solutionblend of: 1) the comparative first ethylene interpolymer (produced withthe third homogeneous catalyst formulation); 2) the second ethyleneinterpolymer, and; 3) optionally the third ethylene interpolymer.

Optimization of Homogeneous Catalyst Formulations

Referring to the first homogeneous catalyst formulation, one embodimentbeing the bridged metallocene catalyst formulation, a highly activeformulation was produced by optimizing the proportion of each of thefour catalyst components: component A, component M, component B andcomponent P. The term “highly active” means the catalyst formulation isvery efficient in converting olefins to polyolefins. In practice theoptimization objective is to maximize the following ratio: (pounds ofethylene interpolymer product produced)/(pounds of catalyst consumed).The quantity of the bulky ligand-metal complex, component A, added to R1was expressed as the parts per million (ppm) of component A in the totalmass of the solution in R1, i.e. “R1 catalyst (ppm)” as recited in Table4A. The upper limit on the ppm of component A may be about 5, in somecases about 3 and is other cases about 2. The lower limit on the ppm ofcomponent A may be about 0.02, in some cases about 0.05 and in othercases about 0.1.

The proportion of catalyst component B, the ionic activator, added to R1was optimized by controlling the (ionic activator)/(component A) molarratio, ([B]/[A]), in the R1 solution. The upper limit on the R1([B]/[A]) may be about 10, in some cases about 5 and in other casesabout 2. The lower limit on R1 ([B]/[A]) may be about 0.3, in some casesabout 0.5 and in other cases about 1.0. The proportion of catalystcomponent M was optimized by controlling the (alumoxane)/(component A)molar ratio, ([M]/[A]), in the R1 solution. The alumoxane co-catalystwas generally added in a molar excess relative to component A. The upperlimit on R1 ([M]/[A]), may be about 300, in some cases about 200 and isother cases about 100. The lower limit on R1 ([M]/[A]), may be about 1,in some cases about 10 and in other cases about 30. The addition ofcatalyst component P (the hindered phenol) to R1 is optional. If added,the proportion of component P was optimized by controlling the (hinderedphenol)/(alumoxane), ([P]/[M]), molar ratio in R1. The upper limit on R1([P]/[M]) may be about 1, in some cases about 0.75 and in other casesabout 0.5. The lower limit on R1 ([P]/[M]) may be 0.0, in some casesabout 0.1 and in other cases about 0.2.

Referring to the second homogeneous catalyst formulation, one embodimentbeing the unbridged single site catalyst formulation, a highly activeformulation was produced by optimizing the proportion of each of thefour catalyst components: component C, component M, component B andcomponent P. Catalyst components M, B and P were independently selectedfor the second homogeneous catalyst formulation, relative to the firsthomogeneous catalyst formulation. To be more clear, components M, B andP in the second homogeneous catalyst formulation may be the samechemical compound, or a different chemical compound, that was used toformulate the first homogeneous catalyst formulation.

The quantity of the bulky ligand metal complex, component C, added to R2was expressed as the parts per million (ppm) of component C in the totalmass of the solution in R2, i.e. “R2 catalyst (ppm)” shown in Table 4A.The upper limit on the R2 ppm of component C may be about 5, in somecases about 3 and is other cases about 2. The lower limit on the R2 ppmof component C may be about 0.02, in some cases about 0.05 and in othercases about 0.1. The proportion of catalyst component B, the ionicactivator, added to R2 was optimized by controlling the (ionicactivator)/(bulky ligand-metal complex) molar ratio, ([B]/[C]), in theR2 solution. The upper limit on R2 ([B]/[C]) may be about 10, in somecases about 5 and in other cases about 2. The lower limit on R2([B]/[C]) may be about 0.3, in some cases about 0.5 and in other casesabout 1.0. The proportion of catalyst component M was optimized bycontrolling the (alumoxane)/(bulky ligand-metal complex) molar ratio,([M]/[C]), in the R2 solution. The alumoxane co-catalyst was generallyadded in a molar excess relative to the bulky ligand-metal complex. Theupper limit on the ([M]/[C]) molar ratio may be about 1000, in somecases about 500 and is other cases about 200. The lower limit on the([M]/[C]) molar ratio may be about 1, in some cases about 10 and inother cases about 30. The addition of catalyst component P to R2 isoptional. If added, the proportion of component P was optimized bycontrolling the (hindered phenol)/(alumoxane) molar ratio, ([P]/[M]), inR2. The upper limit on the R2 ([P]/[M]) molar ratio may be about 1.0, insome cases about 0.75 and in other cases about 0.5. The lower limit onthe R2 ([P]/[M]) molar ratio may be 0.0, in some cases about 0.1 and inother cases about 0.2.

In the case of the third homogeneous catalyst formulation that was usedto synthesize Comparative ethylene interpolymer products a highly activeformulation was produced by optimizing the proportion of each of thefour catalyst components: component C, component M, component B andcomponent P; in a similar fashion to that described above for the secondhomogeneous catalyst formulation.

Additional Solution Polymerization Process Parameters

In the continuous solution processes embodiments shown in FIG. 2 avariety of solvents may be used as the process solvent; non-limitingexamples include linear, branched or cyclic C₅ to C₁₂ alkanes.Non-limiting examples of α-olefins include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene. Suitable catalyst component solventsinclude aliphatic and aromatic hydrocarbons. Non-limiting examples ofaliphatic catalyst component solvents include linear, branched or cyclicC₅₋₁₂ aliphatic hydrocarbons, e.g. pentane, methyl pentane, hexane,heptane, octane, cyclohexane, methylcyclohexane, hydrogenated naphtha orcombinations thereof. Non-limiting examples of aromatic catalystcomponent solvents include benzene, toluene (methylbenzene),ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene(1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures ofxylene isomers, hemellitene (1,2,3-trimethylbenzene), pseudocumene(1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixturesof trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene),durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzeneisomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

It is well known to individuals experienced in the art that reactor feedstreams (solvent, monomer, α-olefin, hydrogen, catalyst formulationetc.) must be essentially free of catalyst deactivating poisons;non-limiting examples of poisons include trace amounts of oxygenatessuch as water, fatty acids, alcohols, ketones and aldehydes. Suchpoisons were removed from reactor feed streams using standardpurification practices; non-limiting examples include molecular sievebeds, alumina beds and oxygen removal catalysts for the purification ofsolvents, ethylene and α-olefins, etc.

Referring to the first and second reactors in FIG. 2 any combination ofthe CSTR reactor feed streams may be heated or cooled: morespecifically, streams 1-4 (reactor 11 a) and streams 6-9 (reactor 12 a).The upper limit on reactor feed stream temperatures may be about 90° C.;in other cases about 80° C. and in still other cases about 70° C. Thelower limit on reactor feed stream temperatures may be about 0° C.; inother cases about 10° C. and in still other cases about 20° C.

Any combination of the streams feeding the tubular reactor may be heatedor cooled; specifically, streams 13-16 in FIG. 2. In some cases, tubularreactor feed streams are tempered, i.e. the tubular reactor feed streamsare heated to at least above ambient temperature. The upper temperaturelimit on the tubular reactor feed streams in some cases are about 200°C., in other cases about 170° C. and in still other cases about 140° C.;the lower temperature limit on the tubular reactor feed streams in somecases are about 60° C., in other cases about 90° C. and in still othercases about 120° C.; with the proviso that the temperature of thetubular reactor feed streams are lower than the temperature of theprocess stream that enters the tubular reactor.

In the embodiments shown in FIG. 2 the operating temperatures of thesolution polymerization reactors (vessels 11 a (R1) and 12 a (R2)) canvary over a wide range. For example, the upper limit on reactortemperatures in some cases may be about 300° C., in other cases about280° C. and in still other cases about 260° C.; and the lower limit insome cases may be about 80° C., in other cases about 100° C. and instill other cases about 125° C. The second reactor, reactor 12 a (R2),is operated at a higher temperature than the first reactor 11 a (R1).The maximum temperature difference between these two reactors(T^(R2)−T^(R1)) in some cases is about 120° C., in other cases about100° C. and in still other cases about 80° C.; the minimum(T^(R2)−T^(R1)) in some cases is about 1° C., in other cases about 5° C.and in still other cases about 10° C. The optional tubular reactor,reactor 17 (R3), may be operated in some cases about 100° C. higher thanR2; in other cases about 60° C. higher than R2, in still other casesabout 10° C. higher than R2 and in alternative cases 0° C. higher, i.e.the same temperature as R2. The temperature within optional R3 mayincrease along its length. The maximum temperature difference betweenthe inlet and outlet of R3 in some cases is about 100° C., in othercases about 60° C. and in still other cases about 40° C. The minimumtemperature difference between the inlet and outlet of R3 is in somecases may be 0° C., in other cases about 3° C. and in still other casesabout 10° C. In some cases R3 is operated an adiabatic fashion and inother cases R3 is heated.

The pressure in the polymerization reactors should be high enough tomaintain the polymerization solution as a single phase solution and toprovide the upstream pressure to force the polymer solution from thereactors through a heat exchanger and on to polymer recovery operations.Referring to the embodiments shown in FIG. 2, the operating pressure ofthe solution polymerization reactors can vary over a wide range. Forexample, the upper limit on reactor pressure in some cases may be about45 MPag, in other cases about 30 MPag and in still other cases about 20MPag; and the lower limit in some cases may be about 3 MPag, in othersome cases about 5 MPag and in still other cases about 7 MPag.

Referring to the embodiments shown in FIG. 2, prior to entering thefirst V/L separator, stream 19, or optionally passivated stream 23 (if aheterogeneous catalyst formulation was employed in reactor 17) may havea maximum temperature in some cases of about 300° C., in other casesabout 290° C. and in still other cases about 280° C.; the minimumtemperature may be in some cases about 150° C., in other cases about200° C. and in still other cases about 220° C. Immediately prior toentering the first V/L separator stream 19, or optionally passivatedstream 23, may have a maximum pressure of about 40 MPag, in other casesabout 25 MPag and in still cases about 15 MPag; the minimum pressure insome cases may be about 1.5 MPag, in other cases about 5 MPag and instill other cases about 6 MPag.

The first V/L separator (vessel 25 in FIG. 2) may be operated over arelatively broad range of temperatures and pressures. For example, themaximum operating temperature of the first V/L separator in some casesmay be about 300° C., in other cases about 285° C. and in still othercases about 270° C.; the minimum operating temperature in some cases maybe about 100° C., in other cases about 140° C. and in still other cases170° C. The maximum operating pressure of the first V/L separator insome cases may be about 20 MPag, in other cases about 10 MPag and instill other cases about 5 MPag; the minimum operating pressure in somecases may be about 1 MPag, in other cases about 2 MPag and in stillother cases about 3 MPag.

The second V/L separator (vessel 28 in FIG. 2) may be operated over arelatively broad range of temperatures and pressures. For example, themaximum operating temperature of the second V/L separator in some casesmay be about 300° C., in other cases about 250° C. and in still othercases about 200° C.; the minimum operating temperature in some cases maybe about 100° C., in other cases about 125° C. and in still other casesabout 150° C. The maximum operating pressure of the second V/L separatorin some cases may be about 1000 kPag, in other cases about 900 kPag andin still other cases about 800 kPag; the minimum operating pressure insome cases may be about 10 kPag, in other cases about 20 kPag and instill other cases about 30 kPag.

The third V/L separator (vessel 31 in FIG. 2) may be operated over arelatively broad range of temperatures and pressures. For example, themaximum operating temperature of the third V/L separator in some casesmay be about 300° C., in other cases about 250° C., and in still othercases about 200° C.; the minimum operating temperature in some cases maybe about 100° C., in other cases about 125° C. and in still other casesabout 150° C. The maximum operating pressure of the third V/L separatorin some cases may be about 500 kPag, in other cases about 150 kPag andin still other cases about 100 kPag; the minimum operating pressure insome cases may be about 1 kPag, in other cases about 10 kPag and instill other cases 25 about kPag.

Embodiments of the continuous solution polymerization process shown inFIG. 2 show three V/L separators. However, continuous solutionpolymerization embodiments may include configurations comprising atleast one V/L separator.

The ethylene interpolymer product produced in the continuous solutionpolymerization process may be recovered using conventionaldevolatilization systems that are well known to persons skilled in theart, non-limiting examples include flash devolatilization systems anddevolatilizing extruders.

Any reactor shape or design may be used for reactor 11 a (R1) andreactor 12 a (R2) in FIG. 2; non-limiting examples include unstirred orstirred spherical, cylindrical or tank-like vessels, as well as tubularreactors or recirculating loop reactors. At commercial scale the maximumvolume of R1 in some cases may be about 20,000 gallons (about 75,710 L),in other cases about 10,000 gallons (about 37,850 L) and in still othercases about 5,000 gallons (about 18,930 L). At commercial scale theminimum volume of R1 in some cases may be about 100 gallons (about 379L), in other cases about 500 gallons (about 1,893 L) and in still othercases about 1,000 gallons (about 3,785 L). At pilot plant scales reactorvolumes are typically much smaller, for example the volume of R1 atpilot scale could be less than about 2 gallons (less than about 7.6 L).In this disclosure the volume of reactor R2 was expressed as a percentof the volume of reactor R1. The upper limit on the volume of R2 in somecases may be about 600% of R1, in other cases about 400% of R1 and instill other cases about 200% of R1. For clarity, if the volume of R1 is5,000 gallons and R2 is 200% the volume of R1, then R2 has a volume of10,000 gallons. The lower limit on the volume of R2 in some cases may beabout 50% of R1, in other cases about 100% of R1 and in still othercases about 150% of R1. In the case of continuously stirred tankreactors the stirring rate can vary over a wide range; in some casesfrom about 10 rpm to about 2000 rpm, in other cases from about 100 toabout 1500 rpm and in still other cases from about 200 to about 1300rpm. In this disclosure the volume of R3, the tubular reactor, wasexpressed as a percent of the volume of reactor R2. The upper limit onthe volume of R3 in some cases may be about 500% of R2, in other casesabout 300% of R2 and in still other cases about 100% of R2. The lowerlimit on the volume of R3 in some cases may be about 3% of R2, in othercases about 10% of R2 and in still other cases about 50% of R2.

The “average reactor residence time”, a commonly used parameter in thechemical engineering art, is defined by the first moment of the reactorresidence time distribution; the reactor residence time distribution isa probability distribution function that describes the amount of timethat a fluid element spends inside the reactor. The average reactorresidence time can vary widely depending on process flow rates andreactor mixing, design and capacity. The upper limit on the averagereactor residence time of the solution in R1 in some cases may be about600 seconds, in other cases about 360 seconds and in still other casesabout 180 seconds. The lower limit on the average reactor residence timeof the solution in R1 in some cases may be about 10 seconds, in othercases about 20 seconds and in still other cases about 40 seconds. Theupper limit on the average reactor residence time of the solution in R2in some cases may be about 720 seconds, in other cases about 480 secondsand in still other cases about 240 seconds. The lower limit on theaverage reactor residence time of the solution in R2 in some cases maybe about 10 seconds, in other cases about 30 seconds and in still othercases about 60 seconds. The upper limit on the average reactor residencetime of the solution in R3 in some cases may be about 600 seconds, inother cases about 360 seconds and in still other cases about 180seconds. The lower limit on the average reactor residence time of thesolution in R3 in some cases may be about 1 second, in other cases about5 seconds and in still other cases about 10 seconds.

Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) couldbe added to the continuous solution polymerization process embodimentsshown in FIG. 2. In this disclosure, the number of reactors was notparticularly important; with the proviso that the continuous solutionpolymerization process comprises at least two reactors that employ afirst homogeneous catalyst formulation and a second homogeneouscatalyst, respectively.

In operating the continuous solution polymerization process embodimentsshown in FIG. 2 the total amount of ethylene supplied to the process canbe portioned or split between the three reactors R1, R2 and R3. Thisoperational variable was referred to as the Ethylene Split (ES), i.e.“ES^(R1)”, “ES^(R2)” and “ES^(R3)” refer to the weight percent ofethylene injected in R1, R2 and R3, respectively; with the proviso thatES^(R1)+ES^(R2)+ES^(R3)=100%. This was accomplished by adjusting theethylene flow rates in the following streams: stream 2 (R1), stream 7(R2) and stream 14 (R3). The upper limit on ES^(R1) in some cases isabout 60%, in other cases about 55% and in still other cases about 50%;the lower limit on ES^(R1) in some cases is about 5%, in other casesabout 8% and in still other cases about 10%. The upper limit on ES^(R2)in some cases is about 95%, in other cases about 92% and in still othercases about 90%; the lower limit on ES^(R2) in some cases is about 20%,in other cases about 30% and in still other cases about 40%. The upperlimit on ES^(R3) in some cases is about 30%, in other cases about 25%and in still other cases about 20%; the lower limit on ES^(R3) in somecases is 0%, in other cases about 5% and in still other cases about 10%.

In operating the continuous solution polymerization process embodimentsshown in FIG. 2 the ethylene concentration in each reactor was alsocontrolled. The ethylene concentration in reactor 1, hereinafterEC^(R1), is defined as the weight of ethylene in reactor 1 divided bythe total weight of everything added to reactor 1; EC^(R2) and EC^(R3)are defined similarly. Ethylene concentrations in the reactors (EC^(R1)or EC^(R2) or EC^(R3)) in some cases may vary from about 7 weightpercent (wt %) to about 25 wt %, in other cases from about 8 wt % toabout 20 wt % and in still other cases from about 9 wt % to about 17 wt%.

In operating the continuous solution polymerization process embodimentsshown in FIG. 2 the total amount of ethylene converted in each reactorwas monitored. The term “Q^(R1)” refers to the percent of the ethyleneadded to R1 that was converted into an ethylene interpolymer by thecatalyst formulation. Similarly Q^(R2) and Q^(R3) represent the percentof the ethylene added to R2 and R3 that was converted into ethyleneinterpolymer, in the respective reactor. Ethylene conversions can varysignificantly depending on a variety of process conditions, e.g.catalyst concentration, catalyst formulation, impurities and poisons.The upper limit on both Q^(R1) and Q^(R2) in some cases is about 99%, inother cases about 95% and in still other cases about 90%; the lowerlimit on both Q^(R1) and Q^(R2) in some cases is about 65%, in othercases about 70% and in still other cases about 75%. The upper limit onQ^(R3) in some cases is about 99%, in other cases about 95% and in stillother cases about 90%; the lower limit on Q^(R3) in some cases is 0%, inother cases about 5% and in still other cases about 10%. The term “QT”represents the total or overall ethylene conversion across the entirecontinuous solution polymerization plant; i.e. Q^(T)=100×[weight ofethylene in the interpolymer product]/([weight of ethylene in theinterpolymer product]+[weight of unreacted ethylene]). The upper limiton Q^(T) in some cases is about 99%, in other cases about 95% and instill other cases about 90%; the lower limit on Q^(T) in some cases isabout 75%, in other cases about 80% and in still other cases about 85%.

Optionally, α-olefin may be added to the continuous solutionpolymerization process. If added, α-olefin may be proportioned or splitbetween R1, R2 and R3. This operational variable was referred to as theComonomer Split (CS), i.e. “CS^(R1)”, “CS^(R2)” and “CS^(R3)” refer tothe weight percent of α-olefin comonomer that is injected in R1, R2 andR3, respectively; with the proviso that CS^(R1)+CS^(R2)+CS^(R3)=100%.This is accomplished by adjusting α-olefin flow rates in the followingstreams: stream 3 (R1), stream 8 (R2) and stream 15 (R3). The upperlimit on CS^(R1) in some cases is 100% (i.e. 100% of the α-olefin isinjected into R1), in other cases about 95% and in still other casesabout 90%. The lower limit on CS^(R1) in some cases is 0% (ethylenehomopolymer produced in R1), in other cases about 5% and in still othercases about 10%. The upper limit on CS^(R2) in some cases is about 100%(i.e. 100% of the α-olefin is injected into reactor 2), in other casesabout 95% and in still other cases about 90%. The lower limit on CS^(R2)in some cases is 0%, in other cases about 5% and in still other casesabout 10%. The upper limit on CS^(R3) in some cases is 100%, in othercases about 95% and in still other cases about 90%. The lower limit onCS^(R3) in some cases is 0%, in other cases about 5% and in still othercases about 10%.

First Ethylene Interpolymer

The first ethylene interpolymer was synthesized using the firsthomogeneous catalyst formulation. One embodiment of the firsthomogeneous catalyst formulation was a bridged metallocene catalystformulation. Referring to the embodiments shown in FIG. 2, if theoptional α-olefin was not added to reactor 1 (R1), then the ethyleneinterpolymer produced in R1 was an ethylene homopolymer. If an α-olefinis added, the following weight ratio was one parameter to control thedensity of the first ethylene interpolymer:((α-olefin)/(ethylene))^(R1). The upper limit on((α-olefin)/(ethylene))^(R1) may be about 3; in other cases about 2 andin still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R1) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereinafter, the symbol “π¹” refers to thedensity of the first ethylene interpolymer produced in R1. The upperlimit on σ¹ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³and; in other cases about 0.955 g/cm³. The lower limit on σ¹ may beabout 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other casesabout 0.875 g/cm³.

Methods to determine the CDBI₅₀ (Composition Distribution BranchingIndex) of an ethylene interpolymer are well known to those skilled inthe art. The CDBI₅₀, expressed as a percent, was defined as the percentof the ethylene interpolymer whose comonomer composition is within 50%of the median comonomer composition. It is also well known to thoseskilled in the art that the CDBI₅₀ of ethylene interpolymers producedwith homogeneous catalyst formulations are higher relative to the CDBI₅₀of α-olefin containing ethylene interpolymers produced withheterogeneous catalyst formulations. The upper limit on the CDBI₅₀ ofthe first ethylene interpolymer may be about 98%, in other cases about95% and in still other cases about 90%. The lower limit on the CDBI₅₀ ofthe first ethylene interpolymer may be about 70%, in other cases about75% and in still other cases about 80%.

The upper limit on the M_(w)/M_(n) (the SEC determined weight averagemolecular weight (M_(w)) divided by the number average molecular weight(M_(n))) of the first ethylene interpolymer may be about 2.8, in othercases about 2.5 and in still other cases about 2.2. The lower limit onthe M_(w)/M_(n) the first ethylene interpolymer may be about 1.7, inother cases about 1.8 and in still other cases about 1.9.

The first ethylene interpolymer, produced with the bridged metallocenecatalyst formulation, contains long chain branching characterized by theLCBF disclosed herein. The upper limit on the LCBF of the first ethyleneinterpolymer may be about 0.5, in other cases about 0.4 and in stillother cases about 0.3 (dimensionless). The lower limit on the LCBF ofthe first ethylene interpolymer may be about 0.001, in other cases about0.0015 and in still other cases about 0.002 (dimensionless).

The first ethylene interpolymer contained catalyst residues that reflectthe chemical composition of the first homogeneous catalyst formulation.Those skilled in the art will understand that catalyst residues aretypically quantified by the parts per million of metal in the firstethylene interpolymer, where metal originates from the metal in catalystcomponent A (Formula (I)); hereinafter this metal will be referred to“metal A”. As recited earlier in this disclosure, non-limiting examplesof metal A include Group 4 metals, titanium, zirconium and hafnium. Theupper limit on the ppm of metal A in the first ethylene interpolymer maybe about 3.0 ppm, in other cases about 2.0 ppm and in still other casesabout 1.5 ppm. The lower limit on the ppm of metal A in the firstethylene interpolymer may be about 0.03 ppm, in other cases about 0.09ppm and in still other cases about 0.15 ppm.

The amount of hydrogen added to R1 can vary over a wide range allowingthe continuous solution process to produce first ethylene interpolymersthat differ greatly in melt index, hereinafter I₂ ¹ (melt index wasmeasured at 190° C. using a 2.16 kg load following the proceduresoutlined in ASTM D1238). This was accomplished by adjusting the hydrogenflow rate in stream 4 (as shown in FIG. 2). The quantity of hydrogenadded to R1 was expressed as the parts-per-million (ppm) of hydrogen inR1 relative to the total mass in reactor R1; hereinafter H₂ ^(R1) (ppm).In some cases H₂ ^(R1) (ppm) ranges from about 100 ppm to 0 ppm, inother cases from about 50 ppm to 0 ppm, in alternative cases from about20 ppm to 0 ppm and in still other cases from about 2 ppm to 0 ppm. Theupper limit on I₂ ¹ may be about 200 dg/min, in some cases about 100dg/min; in other cases about 50 dg/min, and; in still other cases about1 dg/min. The lower limit on I₂ ¹ may be about 0.01 dg/min, in somecases about 0.05 dg/min; in other cases about 0.1 dg/min, and; in stillother cases about 0.5 dg/min.

The upper limit on the weight percent (wt %) of the first ethyleneinterpolymer in the ethylene interpolymer product may be about 60 wt %,in other cases about 55 wt % and in still other cases about 50 wt %. Thelower limit on the wt % of the first ethylene interpolymer in theethylene interpolymer product may be about 5 wt %; in other cases about8 wt % and in still other cases about 10 wt %.

Second Ethylene Interpolymer

The second ethylene interpolymer was synthesized using the secondhomogeneous catalyst formulation. One embodiment of the secondhomogeneous catalyst formulation was an unbridged single site catalystformulation. Referring to the embodiments shown in FIG. 2, if optionalα-olefin was not added to reactor 12 a (R2) either through freshα-olefin stream 8 or carried over from reactor 11 a (R1) in stream 11 e(in series mode), then the ethylene interpolymer produced in reactor 12a (R2) was an ethylene homopolymer. If an optional α-olefin is presentin R2, the following weight ratio was one parameter to control thedensity of the second ethylene interpolymer produced in R2:((α-olefin)/(ethylene))^(R2). The upper limit on((α-olefin)/(ethylene))^(R2) may be about 3; in other cases about 2 andin still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R2) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereinafter, the symbol “σ²” refers to thedensity of the ethylene interpolymer produced in R2. The upper limit onσ² may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; inother cases about 0.955 g/cm³. The lower limit on σ² may be about 0.855g/cm³, in some cases about 0.865 g/cm³, and; in other cases about 0.875g/cm³.

The upper limit on the CDBI₅₀ of the second ethylene interpolymer (thatcontains an α-olefin) may be about 98%, in other cases about 95% and instill other cases about 90%. The lower limit on the CDBI₅₀ of the secondethylene interpolymer may be about 70%, in other cases about 75% and instill other cases about 80%. If an α-olefin is not added to thecontinuous solution polymerization process the second ethyleneinterpolymer was an ethylene homopolymer. In the case of a homopolymer,which does not contain α-olefin, one can still measure a CDBI₅₀ usingTREF. In the case of a homopolymer, the upper limit on the CDBI₅₀ of thesecond ethylene interpolymer may be about 98%, in other cases about 96%and in still other cases about 95%, and; the lower limit on the CDBI₅₀may be about 88%, in other cases about 89% and in still other casesabout 90%. It is well known to those skilled in the art that as theα-olefin content in the second ethylene interpolymer approaches zero,there is a smooth transition between the recited CDBI₅₀ limits for thesecond ethylene interpolymers (that contain an α-olefin) and the recitedCDBI₅₀ limits for the second ethylene interpolymers that are ethylenehomopolymers.

The upper limit on the M_(w)/M_(n) of the second ethylene interpolymermay be about 2.8, in other cases about 2.5 and in still other casesabout 2.2. The lower limit on the M_(w)/M_(n) of the second ethyleneinterpolymer may be about 1.7, in other cases about 1.8 and in stillother cases about 1.9.

The second ethylene interpolymer produced with the second homogeneouscatalyst formulation was characterized by an undetectable level of longchain branching, i.e. LCBF of <0.001 (dimensionless).

The second ethylene interpolymer contains catalyst residues that reflectthe chemical composition of the second homogeneous catalyst formulation.More specifically, the second ethylene interpolymer contains “a metal C”that originates from the bulky ligand-metal complex, i.e. component C(Formula (II)). Non-limiting examples of metal C include Group 4 metals,titanium, zirconium and hafnium. The upper limit on the ppm of metal Cin the second ethylene interpolymer may be about 3.0 ppm, in other casesabout 2.0 ppm and in still other cases about 1.5 ppm. The lower limit onthe ppm of metal C in the second ethylene interpolymer may be about 0.03ppm, in other cases about 0.09 ppm and in still other cases about 0.15ppm.

Referring to the embodiments shown in FIG. 2, the amount of hydrogenadded to R2 can vary over a wide range which allows the continuoussolution process to produce second ethylene interpolymers that differgreatly in melt index, hereinafter I₂ ². This is accomplished byadjusting the hydrogen flow rate in stream 9. The quantity of hydrogenadded was expressed as the parts-per-million (ppm) of hydrogen in R2relative to the total mass in reactor R2; hereinafter H₂ ^(R2) (ppm). Insome cases H₂ ^(R2) (ppm) ranges from about 100 ppm to 0 ppm, in somecases from about 50 ppm to 0 ppm, in other cases from about 20 to 0 andin still other cases from about 2 ppm to 0 ppm. The upper limit on I₂ ²may be about 1000 dg/min; in some cases about 750 dg/min; in other casesabout 500 dg/min, and; in still other cases about 200 dg/min. The lowerlimit on I₂ ² may be about 0.3 dg/min, in some cases about 0.4 dg/min,in other cases about 0.5 dg/min, and; in still other cases about 0.6dg/min.

The upper limit on the weight percent (wt %) of the second ethyleneinterpolymer in the ethylene interpolymer product may be about 95 wt %,in other cases about 92 wt % and in still other cases about 90 wt %. Thelower limit on the wt % of the second ethylene interpolymer in theethylene interpolymer product may be about 20 wt %; in other cases about30 wt % and in still other cases about 40 wt %.

Third Ethylene Interpolymer

Optionally, the disclosed ethylene interpolymer products contain a thirdethylene interpolymer. Referring to the embodiments shown in FIG. 2 athird ethylene interpolymer was not produced in reactor 17 (R3) ifcatalyst deactivator A was added upstream of reactor 17 via catalystdeactivator tank 18A. If catalyst deactivator A was not added andoptional α-olefin was not added to reactor 17 either through freshα-olefin stream 15 or carried over from reactor 12 a (R2) in stream 12 c(series mode) or stream 12 d (parallel mode) then the ethyleneinterpolymer produced in reactor 17 was an ethylene homopolymer. Ifcatalyst deactivator A was not added and optional α-olefin was presentin R3, the following weight ratio was one parameter that determined thedensity of the third ethylene interpolymer:((α-olefin)/(ethylene))^(R3). The upper limit on((α-olefin)/(ethylene))^(R3) may be about 3; in other cases about 2 andin still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R3) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereinafter, the symbol “σ³” refers to thedensity of the ethylene interpolymer produced in R3. The upper limit onσ³ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; inother cases about 0.955 g/cm³. Depending on the catalyst formulationsused in R3, the lower limit on σ³ may be about 0.855 g/cm³, in somecases about 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

Optionally, one or more of the following homogeneous or heterogeneouscatalyst formulations may be injected into R3: the first homogeneouscatalyst formulation, the second homogeneous catalyst formulation, thefifth homogeneous catalyst formulation or the heterogeneous catalystformulation. One embodiment of the first homogeneous catalystformulation was the bridged metallocene catalyst formulation containingcomponent A (Formula (I)), in this case the third ethylene interpolymercontains metal A. The upper limit on the ppm of metal A in the thirdethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppmand in still other cases about 1.5 ppm. The lower limit on the ppm ofmetal A in the third ethylene interpolymer may be about 0.03 ppm, inother cases about 0.09 ppm and in still other cases about 0.15 ppm. Oneembodiment of the second homogeneous catalyst formulation was theunbridged single site catalyst formulation containing component C(Formula (II)), in this case the third ethylene interpolymer containsmetal C. The upper limit on the ppm of metal A in the third ethyleneinterpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and instill other cases about 1.5 ppm. The lower limit on the ppm of metal Ain the third ethylene interpolymer may be about 0.03 ppm, in other casesabout 0.09 ppm and in still other cases about 0.15 ppm. Embodiments ofthe heterogeneous catalyst formulation include an in-line Ziegler-Nattacatalyst formulation or a batch Ziegler-Natta catalyst formulation; inthis case the third ethylene interpolymer contains metal Z thatoriginates from the transition metal compound (component (vii)) used tofabricate the Ziegler-Natta catalyst formulation. The upper limit on theppm of metal Z in the third ethylene interpolymer may be about 12 ppm,in other cases about 10 ppm and in still other cases about 8 ppm. Thelower limit on the ppm of metal Z in the third ethylene interpolymer maybe about 0.5 ppm, in other cases about 1 ppm and in still other casesabout 3 ppm. If the fifth homogeneous catalyst formulation is employed,comprising a bulky ligand-metal complex that is not a member of thegenera defined by Formulas (I) or (II) the third ethylene interpolymercontains metal D. The upper limit on the ppm of metal D in the thirdethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppmand in still other cases about 1.5 ppm. The lower limit on the ppm ofmetal D in the third ethylene interpolymer may be about 0.03 ppm, inother cases about 0.09 ppm and in still other cases about 0.15 ppm.

The upper limit on the CDBI₅₀ of the optional third ethyleneinterpolymer (containing an α-olefin) may be about 98%, in other casesabout 95% and in still other cases about 90%. The lower limit on theCDBI₅₀ of the optional third ethylene interpolymer may be about 35%, inother cases about 40% and in still other cases about 45%.

The upper limit on the M_(w)/M_(n) of the optional third ethyleneinterpolymer may be about 5.0, in other cases about 4.8 and in stillother cases about 4.5. The lower limit on the M_(w)/M_(n) of theoptional third ethylene interpolymer may be about 1.7, in other casesabout 1.8 and in still other cases about 1.9.

Referring to the embodiments shown in FIG. 2, optional hydrogen may beadded to the tubular reactor (R3) via stream 16. The amount of hydrogenadded to R3 may vary over a wide range. Adjusting the amount of hydrogenin R3, hereinafter H₂ ^(R3) (ppm), allows the continuous solutionprocess to produce optional third ethylene interpolymers that differwidely in melt index, hereinafter I₂ ³. The amount of optional hydrogenadded to R3 ranges from about 50 ppm to 0 ppm, in some cases from about25 ppm to 0 ppm, in other cases from about 10 to 0 and in still othercases from about 2 ppm to 0 ppm. The upper limit on I₂ ³ may be about2000 dg/min; in some cases about 1500 dg/min; in other cases about 1000dg/min, and; in still other cases about 500 dg/min. The lower limit onI₂ ³ may be about 0.5 dg/min, in some cases about 0.6 dg/min, in othercases about 0.7 dg/min, and; in still other cases about 0.8 dg/min.

The upper limit on the weight percent (wt %) of the optional thirdethylene interpolymer in the ethylene interpolymer product may be about30 wt %, in other cases about 25 wt % and in still other cases about 20wt %. The lower limit on the wt % of the optional third ethyleneinterpolymer in the ethylene interpolymer product may be 0 wt %; inother cases about 5 wt % and in still other cases about 10 wt %.

Ethylene Interpolymer Product

The upper limit on the density of the ethylene interpolymer product(ρ^(f)) may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and;in other cases about 0.955 g/cm³. The lower limit on the density of theethylene interpolymer product may be about 0.855 g/cm³, in some casesabout 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

The upper limit on the CDBI₅₀ of the ethylene interpolymer product maybe about 97%, in other cases about 90% and in still other cases about85%. An ethylene interpolymer product with a CDBI₅₀ of 97% may result ifan α-olefin is not added to the continuous solution polymerizationprocess; in this case, the ethylene interpolymer product is an ethylenehomopolymer. The lower limit on the CDBI₅₀ of an ethylene interpolymerproduct may be about 1%, in other cases about 2% and in still othercases about 3%.

The upper limit on the M_(w)/M_(n) of the ethylene interpolymer productmay be about 25, in other cases about 15 and in still other cases about9. The lower limit on the M_(w)/M_(n) of the ethylene interpolymerproduct may be 1.7, in other cases about 1.8 and in still other casesabout 1.9.

The catalyst residues in the ethylene interpolymer product reflect thechemical compositions of: the first homogeneous catalyst formulationemployed in R1; the second homogeneous catalyst formulation employed inR2, and; optionally one or more catalyst formulations employed in R3.Catalyst residues were quantified by measuring the parts per million ofcatalytic metal in the ethylene interpolymer products using NeutronActivation Analysis (N.A.A.). As shown in Table 5, the ethyleneinterpolymer product Example 52 contained 0.624 ppm hafnium and 0.208ppm titanium. As shown in Table 4A, Example 52 was produced withreactors 1 and 2 operating in parallel mode, a hafnium (Hf) containingbridged metallocene catalyst formulation was injected into reactor 1 anda titanium (Ti) containing unbridged single site catalyst formulationwas injected into reactor 2 (catalysts were not injected into reactor3). Further, in Example 52, Hf originated from CpF-2 (the[(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] species of component A (Formula (I)) and Tioriginated from PIC-1 (the [Cp[(isopropyl)₃PN]TiCl2] species ofcomponent C (Formula (II)). Example 52 had a residual catalyst Hf/Tiratio of 3.0 (0.624 ppm Hf/0.208 ppm Ti).

As shown in Table 5, the Comparatives contained undetectable levels ofhafnium (0.0 ppm hafnium) and about 0.303 ppm of titanium, i.e. aresidual catalyst Hf/Ti ratio of 0.0. As shown in Table 4A, Comparative60 was produced with reactors 1 and 2 operating in series mode, anunbridged single site catalyst formulation (Ti containing) was injectedinto both reactor 1 and reactor 2 (catalysts were not injected intoreactor 3). In Comparative 60 the Ti source was: PIC-2, thecyclopentadienyl tri(isopropyl) phosphinimine titanium dichloridespecies [Cp[(i-prop)₃PN]TiCl₂] of component C (Formula (II))).

As shown in Table 5, ethylene interpolymer product Example 51 contained0.530 ppm Hf and 0.127 ppm Ti and the residual catalyst Hf/Ti ratio was4.17. As shown in Table 4A, Example 51 was produced with reactors 1 and2 operating in series mode, a Hf containing (CpF-2) bridged metallocenecatalyst formulation was injected into reactor 1 and a Ti containing(PIC-1) unbridged single site catalyst formulation was injected intoreactor 2 (catalysts were not injected into reactor 3).

Comparative 67 contained 0.0 ppm of Hf and about 0.303 ppm Ti and theresidual catalyst Hf/Ti ratio was 0.0. Comparative 67 was produced usingthe unbridged single site catalyst formulation in both reactors 1 and 2.Comparative 67 was a commercially available solution processethylene/1-octene polymer produced by NOVA Chemicals Company (Calgary,Alberta, Canada) coded SURPASS® FPs117-C.

The upper limit on the ppm of metal A in the ethylene interpolymerproduct was determined by maximizing the weight fraction (i.e. 0.60) ofthe first ethylene interpolymer, minimizing the weight fraction (i.e.0.20) of the second ethylene interpolymer and the remaining weightfraction (i.e. 0.20) was the third ethylene interpolymer produced withcatalytic metal A, i.e. the bridged metallocene catalyst formulation.Specifically, the upper limit on the ppm of metal A in the ethyleneinterpolymer product was 2.4 ppm: i.e. ((0.6×3 ppm)+(0.2×3 ppm)); where3 ppm is the upper limit on the ppm of metal A in the first and thirdethylene interpolymers. In other cases, the upper limit on the ppm ofmetal A in the ethylene interpolymer product was 2 ppm and in stillother cases 1.5 ppm. The lower limit on the ppm of metal A in theethylene interpolymer product was determined by minimizing the weightfraction (i.e. 0.05) of the first ethylene interpolymer and maximizingthe weight fraction (i.e. 0.95) of the second ethylene interpolymer.Specifically, the lower limit on the ppm of metal A in the ethyleneinterpolymer product was 0.0015 ppm: i.e. (0.05×0.03 ppm), where 0.03ppm was the lower limit of metal A in the first ethylene interpolymer.In other cases, the lower limit on the ppm of metal A in the ethyleneinterpolymer product was 0.0025 ppm and in still other cases 0.0035 ppm.

The upper limit on the ppm of metal C in the ethylene interpolymerproduct was determined by maximizing the weight fraction (i.e. 0.95) ofthe second ethylene interpolymer, i.e. 2.9 ppm (0.95×3 ppm), where 3 ppmwas the upper limit on the ppm of metal C in the second ethyleneinterpolymer. In other cases, the upper limit on the amount of metal Cin the ethylene interpolymer product was 1.9 ppm and in still othercases 1.4 ppm. The lower limit on the ppm of metal C in the ethyleneinterpolymer product was determined by minimizing the weight fraction(i.e. 0.20) of the second ethylene interpolymer, i.e. 0.006 ppm(0.20×0.03 ppm), where 0.03 ppm was the lower limit on the ppm of metalC in the second ethylene interpolymer. In other cases, the lower limiton the ppm of metal C in the ethylene interpolymer product was 0.02 ppmand in still other cases 0.03 ppm.

The upper limit on the ppm of metal D (originating from the fifthhomogeneous catalyst formulation) in the ethylene interpolymer productwas determined by maximizing the weight fraction (i.e. 0.30) of thethird ethylene interpolymer, i.e. 0.9 ppm (0.3×3 ppm), where 3 ppm isthe upper limit on the ppm of metal D in the third ethyleneinterpolymer. In other cases, the upper limit on the ppm of metal D inthe ethylene interpolymer product was 0.7 ppm and in still other cases0.5 ppm. The lower limit on the ppm of metal D in the ethyleneinterpolymer product was determined by minimizing the weight fraction(i.e. 0.0) of the third ethylene interpolymer, i.e. 0.0 ppm. In othercases when the ethylene interpolymer product contains a small fractionof the third ethylene interpolymer the lower limit on the ppm of metal Din the ethylene interpolymer product may be 0.0015 ppm or 0.003 ppm,i.e. 5 and 10% of the third ethylene interpolymer, respectively.

The upper limit on the ppm of metal Z in the ethylene interpolymerproduct was determined by maximizing the weight fraction (i.e. 0.30) ofthe third ethylene interpolymer, i.e. 3.6 ppm (0.30×12 ppm), where 12ppm was the upper limit on the ppm of metal Z in the third ethyleneinterpolymer. In other cases, the upper limit on amount of metal Z inthe ethylene interpolymer product was 3 ppm and in still other cases 2.4ppm. The lower limit on the ppm of metal Z in the ethylene interpolymerproduct was determined by minimizing the weight fraction (i.e. 0.0) ofthe third ethylene interpolymer, i.e. 0.0 ppm. In other cases where theethylene interpolymer product contains a small fraction of the thirdethylene interpolymer the lower limit on ppm of metal Z in the ethyleneinterpolymer product may be 0.025 ppm and in other cases 0.05 ppm, i.e.5 and 10% of the third ethylene interpolymer, respectively.

The hafnium to titanium ratio (Hf/Ti) in the ethylene interpolymerproduct may range from 400 to 0.0005, as determined by NeutronActivation Analysis. A Hf/Ti ratio of 400 may result in the case of anethylene interpolymer product containing 80 weight % of the a first anda third ethylene interpolymer containing 3 ppm of Hf (upper limit) and20 weight % of a second ethylene interpolymer containing 0.03 ppm of Ti(lower limit). A Hf/Ti ratio of 0.0005 may result in the case of anethylene interpolymer product containing 5 weight % of a first ethyleneinterpolymer containing 0.03 ppm of Hf (lower limit) and 95 weight % ofa second ethylene interpolymer containing 3 ppm of Ti (upper limit).

The upper limit on the total amount of catalytic metal (metal A andmetal C; and optionally metals Z and D) in the ethylene interpolymerproduct may be 6 ppm, in other cases 5 ppm and in still other cases 4ppm. The lower limit on the total amount of catalytic metal in theethylene interpolymer product may be 0.03 ppm, in other cases 0.09 ppmand in still other cases 0.15 ppm.

Embodiments of the ethylene interpolymer products disclosed herein havelower catalyst residues relative the polyethylene polymers described inU.S. Pat. No. 6,277,931. Higher catalyst residues in U.S. Pat. No.6,277,931 increase the complexity of the continuous solutionpolymerization process; an example of increased complexity includesadditional purification steps to remove catalyst residues from thepolymer. In contrast, in the present disclosure, catalyst residues arenot removed.

The upper limit on melt index of the ethylene interpolymer product maybe about 500 dg/min, in some cases about 400 dg/min; in other casesabout 300 dg/min, and; in still other cases about 200 dg/min. The lowerlimit on the melt index of the ethylene interpolymer product may beabout 0.3 dg/min, in some cases about 0.4 dg/min; in other cases about0.5 dg/min, and; in still other cases about 0.6 dg/min.

Catalyst Deactivation

In the continuous polymerization processes described in this disclosure,polymerization is terminated by adding a catalyst deactivator.Embodiments in FIG. 2 show catalyst deactivation occurring either: (a)upstream of the tubular reactor by adding a catalyst deactivator A fromcatalyst deactivator tank 18A, or; (b) downstream of the tubular reactorby adding a catalyst deactivator B from catalyst deactivator tank 18B.Catalyst deactivator tanks 18A and 18B may contain neat (100%) catalystdeactivator, a solution of catalyst deactivator in a solvent, or aslurry of catalyst deactivator in a solvent. The chemical composition ofcatalyst deactivator A and B may be the same, or different. Non-limitingexamples of suitable solvents include linear or branched C₅ to C₁₂alkanes. In this disclosure, how the catalyst deactivator is added isnot particularly important. Once added, the catalyst deactivatorsubstantially stops the polymerization reaction by changing activecatalyst species to inactive forms. Suitable deactivators are well knownin the art, non-limiting examples include: amines (e.g. U.S. Pat. No.4,803,259 to Zboril et al.); alkali or alkaline earth metal salts ofcarboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water(e.g. U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites,alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata);or a combination thereof (U.S. Pat. No. 6,180,730 to Sibtain et al.). Inthis disclosure the quantify of catalyst deactivator added wasdetermined by the following catalyst deactivator molar ratio:0.3≤(catalyst deactivator)/((total catalytic metal)+(alkyl aluminumco-catalyst)+(aluminum alkyl))≤2.0; where the catalytic metal is thetotal moles of (metal A+metal C+any optional catalytic metals added thethird reactor). The upper limit on the catalyst deactivator molar ratiomay be about 2, in some cases about 1.5 and in other cases about 0.75.The lower limit on the catalyst deactivator molar ratio may be about0.3, in some cases about 0.35 and in still other cases about 0.4. Ingeneral, the catalyst deactivator is added in a minimal amount such thatthe catalyst is deactivated and the polymerization reaction is quenched.

Solution Passivation

If a heterogeneous catalyst formulation is employed in the thirdreactor, prior to entering the first V/L separator, a passivator or acidscavenger is added to deactivated solution A or B to form a passivatedsolution, i.e. passivated solution stream 23 as shown in FIG. 2.Passivator tank 22 may contain neat (100%) passivator, a solution ofpassivator in a solvent, or a slurry of passivator in a solvent.Non-limiting examples of suitable solvents include linear or branched C₅to C₁₂ alkanes. In this disclosure, how the passivator is added is notparticularly important. Suitable passivators are well known in the art,non-limiting examples include alkali or alkaline earth metal salts ofcarboxylic acids or hydrotalcites. The quantity of passivator added canvary over a wide range. The quantity of passivator added was determinedby the total moles of chloride compounds added to the solution process,i.e. the chloride compound “compound (vi)” plus the metal compound“compound (vii)” that was used to manufacture the heterogeneous catalystformulation. The upper limit on the (passivator)/(total chlorides) molarratio may be 15, in some cases 13 and in other cases 11. The lower limiton the (passivator)/(total chlorides) molar ratio may be about 5, insome cases about 7 and in still other cases about 9. In general, thepassivator is added in the minimal amount to substantially passivate thedeactivated solution.

Flexible Manufactured Articles

The ethylene interpolymer products disclosed herein may be convertedinto flexible manufactured articles such as monolayer or multilayerfilms. Non-limiting examples of processes to prepare such films includeblown film processes, double bubble processes, triple bubble processes,cast film processes, tenter frame processes and machine directionorientation (MDO) processes.

In the blown film extrusion process an extruder heats, melts, mixes andconveys a thermoplastic, or a thermoplastic blend. Once molten, thethermoplastic is forced through an annular die to produce athermoplastic tube. In the case of co-extrusion, multiple extruders areemployed to produce a multilayer thermoplastic tube. The temperature ofthe extrusion process is primarily determined by the thermoplastic orthermoplastic blend being processed, for example the melting temperatureor glass transition temperature of the thermoplastic and the desiredviscosity of the melt. In the case of polyolefins, typical extrusiontemperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exitfrom the annular die, the thermoplastic tube is inflated with air,cooled, solidified and pulled through a pair of nip rollers. Due to airinflation, the tube increases in diameter forming a bubble of desiredsize. Due to the pulling action of the nip rollers the bubble isstretched in the machine direction. Thus, the bubble is stretched in twodirections: the transverse direction (TD) where the inflating airincreases the diameter of the bubble; and the machine direction (MD)where the nip rollers stretch the bubble. As a result, the physicalproperties of blown films are typically anisotropic, i.e. the physicalproperties differ in the MD and TD directions; for example, film tearstrength and tensile properties typically differ in the MD and TD. Insome prior art documents, the terms “cross direction” or “CD” is used;these terms are equivalent to the terms “transverse direction” or “TD”used in this disclosure. In the blown film process, air is also blown onthe external bubble circumference to cool the thermoplastic as it exitsthe annular die. The final width of the film is determined bycontrolling the inflating air or the internal bubble pressure; in otherwords, increasing or decreasing bubble diameter. Film thickness iscontrolled primarily by increasing or decreasing the speed of the niprollers to control the draw-down rate. After exiting the nip rollers,the bubble or tube is collapsed and may be slit in the machine directionthus creating sheeting. Each sheet may be wound into a roll of film.Each roll may be further slit to create film of the desired width. Eachroll of film is further processed into a variety of consumer products asdescribed below.

The cast film process is similar in that a single or multipleextruder(s) may be used; however the various thermoplastic materials aremetered into a flat die and extruded into a monolayer or multilayersheet, rather than a tube. In the cast film process the extruded sheetis solidified on a chill roll.

In the double bubble process a first blown film bubble is formed andcooled, then the first bubble is heated and re-inflated forming a secondblown film bubble, which is subsequently cooled. The ethyleneinterpolymer products, disclosed herein, are also suitable for thetriple bubble blown process. Additional film converting processes,suitable for the disclosed ethylene interpolymer products, includeprocesses that involve a Machine Direction Orientation (MDO) step; forexample, blowing a film or casting a film, quenching the film and thensubjecting the film tube or film sheet to a MDO process at any stretchratio. Additionally, the ethylene interpolymer product films disclosedherein are suitable for use in tenter frame processes as well as otherprocesses that introduce biaxial orientation.

Depending on the end-use application, the disclosed ethyleneinterpolymer products may be converted into films that span a wide rangeof thicknesses. Non-limiting examples include, food packaging filmswhere thicknesses may range from about 0.5 mil (13 μm) to about 4 mil(102 μm), and; in heavy duty sack applications film thickness may rangefrom about 2 mil (51 μm) to about 10 mil (254 μm).

The monolayer, in monolayer films, may contain more than one ethyleneinterpolymer product and/or one or more additional polymer; non-limitingexamples of additional polymers include ethylene polymers and propylenepolymers. The lower limit on the weight percent of the ethyleneinterpolymer product in a monolayer film may be about 3 wt %, in othercases about 10 wt % and in still other cases about 30 wt %. The upperlimit on the weight percent of the ethylene interpolymer product in themonolayer film may be 100 wt %, in other cases about 90 wt % and instill other cases about 70 wt %.

The ethylene interpolymer products disclosed herein may also be used inone or more layers of a multilayer film; non-limiting examples ofmultilayer films include three, five, seven, nine, eleven or morelayers. The disclosed ethylene interpolymer products are also suitablefor use in processes that employ micro-layering dies and/or feedblocks,such processes can produce films having many layers, non-limitingexamples include from 10 to 10,000 layers.

The thickness of a specific layer (containing the ethylene interpolymerproduct) within a multilayer film may be about 5%, in other cases about15% and in still other cases about 30% of the total multilayer filmthickness. In other embodiments, the thickness of a specific layer(containing the ethylene interpolymer product) within a multilayer filmmay be about 95%, in other cases about 80% and in still other casesabout 65% of the total multilayer film thickness. Each individual layerof a multilayer film may contain more than one ethylene interpolymerproduct and/or additional thermoplastics.

Additional embodiments include laminations and coatings, wherein mono ormultilayer films containing the disclosed ethylene interpolymer productsare extrusion laminated or adhesively laminated or extrusion coated. Inextrusion lamination or adhesive lamination, two or more substrates arebonded together with a thermoplastic or an adhesive, respectively. Inextrusion coating, a thermoplastic is applied to the surface of asubstrate. These processes are well known to those experienced in theart. Frequently, adhesive lamination or extrusion lamination are used tobond dissimilar materials, non-limiting examples include the bonding ofa paper web to a thermoplastic web, or the bonding of an aluminum foilcontaining web to a thermoplastic web, or the bonding of twothermoplastic webs that are chemically incompatible, e.g. the bonding ofan ethylene interpolymer product containing web to a polyester orpolyamide web. Prior to lamination, the web containing the disclosedethylene interpolymer product(s) may be monolayer or multilayer. Priorto lamination the individual webs may be surface treated to improve thebonding, a non-limiting example of a surface treatment is coronatreating. A primary web or film may be laminated on its upper surface,its lower surface, or both its upper and lower surfaces with a secondaryweb. A secondary web and a tertiary web could be laminated to theprimary web; wherein the secondary and tertiary webs differ in chemicalcomposition. As non-limiting examples, secondary or tertiary webs mayinclude; polyamide, polyester and polypropylene, or webs containingbarrier resin layers such as EVOH. Such webs may also contain a vapordeposited barrier layer; for example a thin silicon oxide (SiO_(x)) oraluminum oxide (AlO_(x)) layer. Multilayer webs (or films) may containthree, five, seven, nine, eleven or more layers.

The ethylene interpolymer products disclosed herein can be used in awide range of manufactured articles comprising one or more films(monolayer or multilayer). Non-limiting examples of such manufacturedarticles include: food packaging films (fresh and frozen foods, liquidsand granular foods), stand-up pouches, retortable packaging andbag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.)and modified atmosphere packaging; light and heavy duty shrink films andwraps, collation shrink film, pallet shrink film, shrink bags, shrinkbundling and shrink shrouds; light and heavy duty stretch films, handstretch wrap, machine stretch wrap and stretch hood films; high clarityfilms; heavy-duty sacks; household wrap, overwrap films and sandwichbags; industrial and institutional films, trash bags, can liners,magazine overwrap, newspaper bags, mail bags, sacks and envelopes,bubble wrap, carpet film, furniture bags, garment bags, coin bags, autopanel films; medical applications such as gowns, draping and surgicalgarb; construction films and sheeting, asphalt films, insulation bags,masking film, landscaping film and bags; geomembrane liners formunicipal waste disposal and mining applications; batch inclusion bags;agricultural films, mulch film and green house films; in-storepackaging, self-service bags, boutique bags, grocery bags, carry-outsacks and t-shirt bags; oriented films, machine direction oriented (MDO)films, biaxially oriented films and functional film layers in orientedpolypropylene (OPP) films, e.g. sealant and/or toughness layers.Additional manufactured articles comprising one or more films containingat least one ethylene interpolymer product include laminates and/ormultilayer films; sealants and tie layers in multilayer films andcomposites; laminations with paper; aluminum foil laminates or laminatescontaining vacuum deposited aluminum; polyamide laminates; polyesterlaminates; extrusion coated laminates, and; hot-melt adhesiveformulations. The manufactured articles summarized in this paragraphcontain at least one film (monolayer or multilayer) comprising at leastone embodiment of the disclosed ethylene interpolymer products.

Desired film physical properties (monolayer or multilayer) typicallydepend on the application of interest. Non-limiting examples ofdesirable film properties include: optical properties (gloss, haze andclarity), dart impact, Elmendorf tear, modulus (1% and 2% secantmodulus), tensile properties (yield strength, break strength, elongationat break, toughness, etc.), heat sealing properties (heat sealinitiation temperature, SIT, and hot tack). Specific hot tack and heatsealing properties are desired in high speed vertical and horizontalform-fill-seal processes that load and seal a commercial product(liquid, solid, paste, part, etc.) inside a pouch-like package.

In addition to desired film physical properties, it is desired that thedisclosed ethylene interpolymer products are easy to process on filmlines. Those skilled in the art frequently use the term “processability”to differentiate polymers with improved processability, relative topolymers with inferior processability. A commonly used measure toquantify processability is extrusion pressure; more specifically, apolymer with improved processability has a lower extrusion pressure (ona blown film or a cast film extrusion line) relative to a polymer withinferior processability.

The films used in the manufactured articles described in this sectionmay optionally include, depending on its intended use, additives andadjuvants. Non-limiting examples of additives and adjuvants include,anti-blocking agents, antioxidants, heat stabilizers, slip agents,processing aids, anti-static additives, colorants, dyes, fillermaterials, light stabilizers, light absorbers, lubricants, pigments,plasticizers, nucleating agents and combinations thereof.

Rigid Manufactured Articles

The processes disclosed herein are also capable of making ethyleneinterpolymer products that have a useful combination of desirablephysical properties for use in rigid manufactured articles. Non-limitingexamples of rigid articles include: deli containers, margarine tubs,drink cups and produce trays; household and industrial containers, cups,bottles, pails, crates, tanks, drums, bumpers, lids, industrial bulkcontainers, industrial vessels, material handling containers, bottle capliners, bottle caps, living hinge closures; toys, playground equipment,recreational equipment, boats, marine and safety equipment; wire andcable applications such as power cables, communication cables andconduits; flexible tubing and hoses; pipe applications including bothpressure pipe and non-pressure pipe markets, e.g. natural gasdistribution, water mains, interior plumbing, storm sewer, sanitarysewer, corrugated pipes and conduit; foamed articles manufactured fromfoamed sheet or bun foam; military packaging (equipment and readymeals); personal care packaging, diapers and sanitary products;cosmetic, pharmaceutical and medical packaging, and; truck bed liners,pallets and automotive dunnage. The rigid manufactured articlessummarized in this paragraph contain one or more of the ethyleneinterpolymer products disclosed herein or a blend of at least one of theethylene interpolymer products disclosed herein with at least one otherthermoplastic.

Such rigid manufactured articles may be fabricated using the followingnon-limiting processes: injection molding, compression molding, blowmolding, rotomolding, profile extrusion, pipe extrusion, sheetthermoforming and foaming processes employing chemical or physicalblowing agents.

The desired physical properties of rigid manufactured articles depend onthe application of interest. Non-limiting examples of desired propertiesinclude: flexural modulus (1% and 2% secant modulus); tensile toughness;environmental stress crack resistance (ESCR); slow crack growthresistance (PENT); abrasion resistance; shore hardness; deflectiontemperature under load; VICAT softening point; IZOD impact strength; ARMimpact resistance; Charpy impact resistance, and; color (whitenessand/or yellowness index).

The rigid manufactured articles described in this section may optionallyinclude, depending on its intended use, additives and adjuvants.Non-limiting examples of additives and adjuvants include, antioxidants,slip agents, processing aids, anti-static additives, colorants, dyes,filler materials, heat stabilizers, light stabilizers, light absorbers,lubricants, pigments, plasticizers, nucleating agents and combinationsthereof.

Testing Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2° C. and 50±10% relative humidity and subsequent testing wasconducted at 23±2° C. and 50±10% relative humidity. Herein, the term“ASTM conditions” refers to a laboratory that is maintained at 23±2° C.and 50±10% relative humidity; and specimens to be tested wereconditioned for at least 24 hours in this laboratory prior to testing.ASTM refers to the American Society for Testing and Materials.

Density

Ethylene interpolymer product densities were determined using ASTMD792-13 (Nov. 1, 2013).

Melt Index

Ethylene interpolymer product melt index was determined using ASTM D1238(Aug. 1, 2013). Melt indexes, I₂, I₆, I₁₀ and I₂₁ were measured at 190°C., using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively.Herein, the term “stress exponent” or its acronym “S.Ex.”, is defined bythe following relationship:S.Ex.=log(I ₆ /I ₂)/log(6480/2160)wherein I₆ and I₂ are the melt flow rates measured at 190° C. using 6.48kg and 2.16 kg loads, respectively.Conventional Size Exclusion Chromatography (SEC)

Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. An antioxidant(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture inorder to stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Polymer solutions were chromatographed at140° C. on a PL 220 high-temperature chromatography unit equipped withfour Shodex columns (HT803, HT804, HT805 and HT806) using TCB as themobile phase with a flow rate of 1.0 mL/minute, with a differentialrefractive index (DRI) as the concentration detector. BHT was added tothe mobile phase at a concentration of 250 ppm to protect GPC columnsfrom oxidative degradation. The sample injection volume was 200 μL. TheGPC columns were calibrated with narrow distribution polystyrenestandards. The polystyrene molecular weights were converted topolyethylene molecular weights using the Mark-Houwink equation, asdescribed in the ASTM standard test method D6474-12 (December 2012). TheGPC raw data were processed with the Cirrus GPC software, to producemolar mass averages (M_(n), M_(w), M_(z)) and molar mass distribution(e.g. Polydispersity, M_(w)/M_(n)). In the polyethylene art, a commonlyused term that is equivalent to SEC is GPC, i.e. Gel PermeationChromatography.

Triple Detection Size Exclusion Chromatography (3D-SEC)

Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. An antioxidant(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture inorder to stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with adifferential refractive index (DRI) detector, a dual-angle lightscattering detector (15 and 90 degree) and a differential viscometer.The SEC columns used were either four Shodex columns (HT803, HT804,HT805 and HT806), or four PL Mixed ALS or BLS columns. TCB was themobile phase with a flow rate of 1.0 mL/minute, BHT was added to themobile phase at a concentration of 250 ppm to protect SEC columns fromoxidative degradation. The sample injection volume was 200 μL. The SECraw data were processed with the Cirrus GPC software, to produceabsolute molar masses and intrinsic viscosity ([η]). The term “absolute”molar mass was used to distinguish 3D-SEC determined absolute molarmasses from the molar masses determined by conventional SEC. Theviscosity average molar mass (M_(v)) determined by 3D-SEC was used inthe calculations to determine the Long Chain Branching Factor (LCBF).

GPC-FTIR

Ethylene interpolymer product (polymer) solutions (2 to 4 mg/mL) wereprepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a Waters GPC 150C chromatography unit equipped with four Shodexcolumns (HT803, HT804, HT805 and HT806) using TCB as the mobile phasewith a flow rate of 1.0 mL/minute, with a FTIR spectrometer and a heatedFTIR flow through cell coupled with the chromatography unit through aheated transfer line as the detection system. BHT was added to themobile phase at a concentration of 250 ppm to protect SEC columns fromoxidative degradation. The sample injection volume was 300 μL. The rawFTIR spectra were processed with OPUS FTIR software and the polymerconcentration and methyl content were calculated in real time with theChemometric Software (PLS technique) associated with the OPUS. Then thepolymer concentration and methyl content were acquired andbaseline-corrected with the Cirrus GPC software. The SEC columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474. The comonomer content was calculated basedon the polymer concentration and methyl content predicted by the PLStechnique as described in Paul J. DesLauriers, Polymer 43, pages 159-170(2002); herein incorporated by reference.

The GPC-FTIR method measures total methyl content, which includes themethyl groups located at the ends of each macromolecular chain, i.e.methyl end groups. Thus, the raw GPC-FTIR data must be corrected bysubtracting the contribution from methyl end groups. To be more clear,the raw GPC-FTIR data overestimates the amount of short chain branching(SCB) and this overestimation increases as molecular weight (M)decreases. In this disclosure, raw GPC-FTIR data was corrected using the2-methyl correction. At a given molecular weight (M), the number ofmethyl end groups (N_(E)) was calculated using the following equation;N_(E)=28000/M, and N_(E) (M dependent) was subtracted from the rawGPC-FTIR data to produce the SCB/1000 C (2-Methyl Corrected) GPC-FTIRdata.

Composition Distribution Branching Index (CDBI)

The “Composition Distribution Branching Index”, hereinafter CDBI, of thedisclosed Examples and Comparative Examples were measured using aCRYSTAF/TREF 200+ unit equipped with an IR detector, hereinafter theCTREF. The acronym “TREF” refers to Temperature Rising ElutionFractionation. The CTREF was supplied by PolymerChAR S.A. (ValenciaTechnology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain).The CTREF was operated in the TREF mode, which generates the chemicalcomposition of the polymer sample as a function of elution temperature,the Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI (theComposition Distribution Breadth Index), i.e. CDBI₅₀ and CDBI₂₅. Apolymer sample (80 to 100 mg) was placed into the reactor vessel of theCTREF. The reactor vessel was filled with 35 ml of1,2,4-trichlorobenzene (TCB) and the polymer was dissolved by heatingthe solution to 150° C. for 2 hours. An aliquot (1.5 mL) of the solutionwas then loaded into the CTREF column which was packed with stainlesssteel beads. The column, loaded with sample, was allowed to stabilize at110° C. for 45 minutes. The polymer was then crystallized from solution,within the column, by dropping the temperature to 30° C. at a coolingrate of 0.09° C./minute. The column was then equilibrated for 30 minutesat 30° C. The crystallized polymer was then eluted from the column withTCB flowing through the column at 0.75 mL/minute, while the column wasslowly heated from 30° C. to 120° C. at a heating rate of 0.25°C./minute. The raw CTREF data were processed using Polymer ChARsoftware, an Excel spreadsheet and CTREF software developed in-house.CDBI₅₀ was defined as the percent of polymer whose composition is within50% of the median comonomer composition; CDBI₅₀ was calculated from thecomposition distribution cure and the normalized cumulative integral ofthe composition distribution curve, as described in U.S. Pat. No.5,376,439. Those skilled in the art will understand that a calibrationcurve is required to convert a CTREF elution temperature to comonomercontent, i.e. the amount of comonomer in the ethylene/α-olefin polymerfraction that elutes at a specific temperature. The generation of suchcalibration curves are described in the prior art, e.g. Wild, et al., J.Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: herebyfully incorporated by reference. CDBI₂₅ as calculated in a similarmanner; CDBI₂₅ is defined as the percent of polymer whose composition iswith 25% of the median comonomer composition. At the end of each samplerun, the CTREF column was cleaned for 30 minutes; specifically, with theCTREF column temperature at 160° C., TCB flowed (0.5 mL/minute) throughthe column for 30 minutes. CTREF deconvolutions were performed todetermine the amount of branching (BrF (#C6/1000 C)) and density of thefirst ethylene interpolymer using the following equations: BrF (#C₆/1000C)=74.29-0.7598 (T^(P) _(CTREF)), where T^(P) _(CTREF) is the peakelution temperature of the first ethylene interpolymer in the CTREFchromatogram, and BrF (#C₆/1000 C)=9341.8 (ρ¹)²−17766 (ρ¹)+8446.8, whereρ¹ was the density of the first ethylene interpolymer. The BrF (#C₆/1000C) and density of the second ethylene interpolymer was determined usingblending rules, given the overall BrF (#C₆/1000 C) and density of theethylene interpolymer product. The BrF (#C₆/1000 C) and density of thesecond and third ethylene interpolymer was assumed to be the same.

Neutron Activation (Elemental Analysis)

Neutron Activation Analysis, hereinafter N.A.A., was used to determinecatalyst residues in ethylene interpolymer products as follows. Aradiation vial (composed of ultrapure polyethylene, 7 mL internalvolume) was filled with an ethylene interpolymer product sample and thesample weight was recorded. Using a pneumatic transfer system the samplewas placed inside a SLOWPOKE™ nuclear reactor (Atomic Energy of CanadaLimited, Ottawa, Ontario, Canada) and irradiated for 30 to 600 secondsfor short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5hours for long half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). Theaverage thermal neutron flux within the reactor was 5×10¹¹/cm²/s. Afterirradiation, samples were withdrawn from the reactor and aged, allowingthe radioactivity to decay; short half-life elements were aged for 300seconds or long half-life elements were aged for several days. Afteraging, the gamma-ray spectrum of the sample was recorded using agermanium semiconductor gamma-ray detector (Ortec model GEM55185,Advanced Measurement Technology Inc., Oak Ridge, Tenn., USA) and amultichannel analyzer (Ortec model DSPEC Pro). The amount of eachelement in the sample was calculated from the gamma-ray spectrum andrecorded in parts per million relative to the total weight of theethylene interpolymer product sample. The N.A.A. system was calibratedwith Specpure standards (1000 ppm solutions of the desired element(greater than 99% pure)). One mL of solutions (elements of interest)were pipetted onto a 15 mm×800 mm rectangular paper filter and airdried. The filter paper was then placed in a 1.4 mL polyethyleneirradiation vial and analyzed by the N.A.A. system. Standards are usedto determine the sensitivity of the N.A.A. procedure (in counts/μg).

Unsaturation

The quantity of unsaturated groups, i.e. double bonds, in an ethyleneinterpolymer product was determined according to ASTM D3124-98(vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyland trans unsaturation, published July 2012). An ethylene interpolymerproduct sample was: a) first subjected to a carbon disulfide extractionto remove additives that may interfere with the analysis; b) the sample(pellet, film or granular form) was pressed into a plaque of uniformthickness (0.5 mm), and; c) the plaque was analyzed by FTIR.

Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy

The quantity of comonomer in an ethylene interpolymer product wasdetermine by FTIR and reported as the Short Chain Branching (SCB)content having dimensions of CH₃#/1000 C (number of methyl branches per1000 carbon atoms). This test was completed according to ASTM D6645-01(2001), employing a compression molded polymer plaque and aThermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plaque wasprepared using a compression molding device (Wabash-Genesis Seriespress) according to ASTM D4703-16 (April 2016).

Dynamic Mechanical Analysis (DMA)

Oscillatory shear measurements under small strain amplitudes werecarried out to obtain linear viscoelastic functions at 190° C. under N₂atmosphere, at a strain amplitude of 10% and over a frequency range of0.02-126 rad/s at 5 points per decade. Frequency sweep experiments wereperformed with a TA Instruments DHR3 stress-controlled rheometer usingcone-plate geometry with a cone angle of 5°, a truncation of 137 μm anda diameter of 25 mm. In this experiment a sinusoidal strain wave wasapplied and the stress response was analyzed in terms of linearviscoelastic functions. The zero shear rate viscosity (η₀) based on theDMA frequency sweep results was predicted by Ellis model (see R. B. Birdet al. “Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics”Wiley-Interscience Publications (1987) p. 228) or Carreau-Yasuda model(see K. Yasuda (1979) PhD Thesis, IT Cambridge). In this disclosure, theLCBF (Long Chain Branching Factor) was determined using the DMAdetermined η₀.

Creep Test

Creep measurements were performed by an Anton Paar MCR 501 rheometer at190° C. using 25 mm parallel plate geometry under N₂ atmosphere. In thisexperiment, a compression molded circular plaque with a thickness of 1.8mm was placed between the pre-heated upper and lower measurementfixtures and allowed to come to thermal equilibrium. The upper plate wasthen lowered to 50 μm above the testing gap size of 1.5 mm. At thispoint, the excess material was trimmed off and the upper fixture waslowered to the measurement gap size. A waiting time of 10 min aftersample loading and trimming was applied to avoid residual stressescausing the strain to drift. In the creep experiment, the shear stresswas increased instantly from 0 to 20 Pa and the strain was recordedversus time. The sample continued to deform under the constant shearstress and eventually reached a steady rate of straining. Creep data wasreported in terms of creep compliance (J(t)) which has the units ofreciprocal modulus. The inverse of J(t) slope in the steady creepingregime was used to calculate the zero shear rate viscosity based on thelinear regression of the data points in the last 10% time window of thecreep experiment.

In order to determine if the sample was degraded during the creep test,frequency sweep experiments under small strain amplitude (10%) wereperformed before and after creep stage over a frequency range of 0.1-100rad/s. The difference between the magnitude of complex viscosity at 0.1rad/s before and after the creep stage was used as an indicator ofthermal degradation. The difference should be less than 5% to considerthe creep determined zero shear rate viscosity acceptable.

Creep experiments confirmed that Reference Line, shown in FIG. 1, forlinear ethylene interpolymers was also valid if the creep determined η₀was used rather than the DMA determined η₀. In this disclosure, the LCBF(Long Chain Branching Factor) was determined using the DMA determinedη₀. To be absolutely clear, the zero shear viscosity (ZSV [poise]) datareported in Tables 1A, 2 and 3 were measured using DMA.

¹³C Nuclear Magnetic Resonance (NMR)

Between 0.21 and 0.30 g of polymer sample was weighed into 10 mm NMRtubes. The sample was then dissolved with deuteratedortho-dichlorobenzene (ODCB-d4) and heated to 125° C.; a heat gun wasused to assist the mixing process. ¹³C NMR spectra (24000 scans perspectra) were collected on a Bruker AVANCE III HD 400 MHz NMRspectrometer fitted with a 10 mm PABBO probehead maintained at 125° C.Chemical shifts were referenced to the polymer backbone resonance, whichwas assigned a value of 30.0 ppm. ¹³C spectra were processed usingexponential multiplication with a line broadening (LB) factor of 1.0 Hz.They were also processed using Gaussian multiplication with LB=−0.5 Hzand GB=0.2 to enhance resolution.

Short chain branching was calculated using the isolated method, wherethe integral area of peaks unique to that branch length are compared tothe total integral (standard practice for branches up to and includingC5). Quantitative data for the C1, C2, C3, C4, (C6+LCB) and theSaturated Termini (Sat. Term.) carbons was presented in Table 14, allvalues reported per 1000 total carbon atoms, data accuracy was ±0.03branches/1000 C. Any values of 0.03 branches/1000 C or less were assumedbeyond the ability to quantify and were marked with a ‘D’ to indicatethat a peak was detected but not quantifiable in Table 14.

FIG. 3 diagrams a long chain branched macromolecule on the left and a C₆branched macromolecule on the right and the nomenclature, or code, usedto identify each carbon atom that appears in the ¹³C-NMR spectrum ofthese macromolecules. Branchpoint carbons peaks (CH_((L)) and CH₍₆₎,38.2 ppm), as well as the 1B_(L)/1B₆, 2B_(L)/2B₆ and 3B_(L)/3B₆ carbonpeaks (at 14.1, 22.9, and 32.2 ppm, respectively) are close together inthe spectrum. Additionally, the ends of a LCB are functionallyequivalent to the ends of macromolecular chains. In ethylene-octenecopolymers there was separation between the 2B₆ and 3B₆ peaks and the 2s& 3s peaks in the chain termini. With the goal of deconvoluting the C6and LCB contributions to the branchpoint peak (38.2 ppm), the spectrawere reprocessed using a Gaussian function (as opposed to an exponentialfunction), specifically LB=−0.5 and GB=0.2. The net effect of thisreprocessing was to ‘trade off’ some signal/noise (S/N) for additionalresolution without negatively impacting peak integration, i.e.quantification of the respective carbons. Using this technique, thevalues for C6, LCB and saturated termini were obtained using thefollowing method: 1) the values for (C6+LCB) peak at 38.2 ppm and thetwo (LCB+sat. term.) peaks at 32.2 and 22.9 ppm were calculated from the‘standard’ spectrum; 2) these three peak regions in the Gaussianreprocessed spectra (i.e. 38.2, 32.2 and 22.9 ppm) were integrated toobtain a ratio for each carbon within the respective peak; 3) theseratios were converted to a value per 1000 carbons by normalizing by therespective integrated area measured in step 1); 4) the saturated terminiwas the average of that from 2s & 3s peaks; 5) the C6 value wasestimated from the integrals of the small peaks on the far left of thesethree regions, and; 6) the LCB value was estimated from the peak at 38.2ppm.

Film Dart Impact

Film dart impact strength was determined using ASTM D1709-09 Method A(May 1, 2009). In this disclosure the dart impact test employed a 1.5inch (38 mm) diameter hemispherical headed dart.

Film Puncture

Film “puncture”, the energy (J/mm) required to break the film wasdetermined using ASTM D5748-95 (originally adopted in 1995, reapprovedin 2012).

Film Lubricated Puncture

The “lubricated puncture” test was performed as follows: the energy(J/mm) to puncture a film sample was determined using a 0.75-inch(1.9-cm) diameter pear-shaped fluorocarbon coated probe travelling at10-inch per minute (25.4-cm/minute). ASTM conditions were employed.Prior to testing the specimens, the probe head was manually lubricatedwith Muko Lubricating Jelly to reduce friction. Muko Lubricating Jellyis a water-soluble personal lubricant available from Cardinal HealthInc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mountedin an Instron Model 5 SL Universal Testing Machine and a 1000-N loadcell as used. Film samples (1.0 mil (25 μm) thick, 5.5 inch (14 cm) wideand 6 inch (15 cm) long) were mounted in the Instron and punctured.

Film Tensile

The following film tensile properties were determined using ASTM D882-12(Aug. 1, 2012): tensile break strength (MPa), elongation at break (%),tensile yield strength (MPa), tensile elongation at yield (%) and filmtoughness or total energy to break (ft·lb/in³). Tensile properties weremeasured in the both the machine direction (MD) and the transversedirection (TD) of the blown films.

Film Secant Modulus

The secant modulus is a measure of film stiffness. Secant moduli weredetermined according to ASTM D882. The secant modulus is the slope of aline drawn between two points on the stress-strain curve, i.e. thesecant line. The first point on the stress-strain curve is the origin,i.e. the point that corresponds to the origin (the point of zero percentstrain and zero stress), and; the second point on the stress-straincurve is the point that corresponds to a strain of 1%; given these twopoints the 1% secant modulus is calculated and is expressed in terms offorce per unit area (MPa). The 2% secant modulus is calculatedsimilarly. This method is used to calculated film modulus because thestress-strain relationship of polyethylene does not follow Hook's law;i.e. the stress-strain behavior of polyethylene is non-linear due to itsviscoelastic nature. Secant moduli were measured using a conventionalInstron tensile tester equipped with a 200 lbf load cell. Strips ofmonolayer film samples were cut for testing with following dimensions:14 inch long, 1 inch wide and 1 mil thick; ensuring that there were nonicks or cuts on the edges of the samples. Film samples were cut in boththe machine direction (MD) and the transverse direction (TD) and tested.ASTM conditions were used to condition the samples. The thickness ofeach film was accurately measured with a hand-held micrometer andentered along with the sample name into the Instron software. Sampleswere loaded in the Instron with a grip separation of 10 inch and pulledat a rate of 1 inch/min generating the strain-strain curve. The 1% and2% secant modulus were calculated using the Instron software.

Film Puncture-Propagation Tear

Puncture-propagation tear resistance of blown film was determined usingASTM D2582-09 (May 1, 2009). This test measures the resistance of ablown film to snagging, or more precisely, to dynamic puncture andpropagation of that puncture resulting in a tear. Puncture-propagationtear resistance was measured in the machine direction (MD) and thetransverse direction (TD) of the blown films.

Film Elmendorf Tear

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); anequivalent term for tear is “Elmendorf tear”. Film tear was measured inboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film Opticals

Film optical properties were measured as follows: Haze, ASTM D1003-13(Nov. 15, 2013), and; Gloss ASTM D2457-13 (Apr. 1, 2013).

Film Dynatup Impact

Instrumented impact testing was carried out on a machine called aDynatup Impact Tester purchased from Illinois Test Works Inc., SantaBarbara, Calif., USA; those skilled in the art frequently call this testthe Dynatup impact test. Testing was completed according to thefollowing procedure. Test samples are prepared by cutting about 5 inch(12.7 cm) wide and about 6 inch (15.2 cm) long strips from a roll ofblown film; film was about 1 mil thick. Prior to testing, the thicknessof each sample was accurately measured with a handheld micrometer andrecorded. ASTM conditions were employed. Test samples were mounted inthe 9250 Dynatup Impact drop tower/test machine using the pneumaticclamp. Dynatup tup #1, 0.5 inch (1.3 cm) diameter, was attached to thecrosshead using the Allen bolt supplied. Prior to testing, the crossheadis raised to a height such that the film impact velocity is 10.9±0.1ft/s. A weight was added to the crosshead such that: 1) the crossheadslowdown, or tup slowdown, was no more than 20% from the beginning ofthe test to the point of peak load and 2) the tup must penetrate throughthe specimen. If the tup does not penetrate through the film, additionalweight is added to the crosshead to increase the striking velocity.During each test the Dynatup Impulse Data Acquisition System Softwarecollected the experimental data (load (lb) versus time). At least 5 filmsamples are tested and the software reports the following averagevalues: “Dynatup Maximum (Max) Load (lb)”, the highest load measuredduring the impact test; “Dynatup Total Energy (ft·lb)”, the area underthe load curve from the start of the test to the end of the test(puncture of the sample), and; “Dynatup Total Energy at Max Load(ft·lb)”, the area under the load curve from the start of the test tothe maximum load point.

Film Hot Tack

In this disclosure, the “Hot Tack Test” was performed as follows, usingASTM conditions. Hot tack data was generated using a J&B Hot Tack Testerwhich is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630Maamechelen, Belgium. In the hot tack test, the strength of a polyolefinto polyolefin seal is measured immediately after heat sealing two filmsamples together (the two film samples were cut from the same roll of2.0 mil (51-μm) thick film), i.e. when the polyolefin macromoleculesthat comprise the film are in a semi-molten state. This test simulatesthe heat sealing of polyethylene films on high speed automatic packagingmachines, e.g., vertical or horizontal form, fill and seal equipment.The following parameters were used in the J&B Hot Tack Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 0.27 N/mm²; delay time, 0.5 second; film peel speed,7.9 in/second (200 mm/second); testing temperature range, 203° F. to293° F. (95° C. to 145° C.); temperature increments, 9° F. (5° C.); andfive film samples were tested at each temperature increment to calculateaverage values at each temperature. The following data was recorded forthe disclosed Example films and Comparative Example films: the “TackOnset @ 1.0 N (° C.)”, the temperature at which a hot tack force of 1Nwas observed (average of 5-film samples); “Max Hot tack Strength (N)”,the maximum hot tack force observed (average of 5-film samples) over thetesting temperature range, and; “Temperature—Max. Hot tack (° C.)”, thetemperature at which the maximum hot tack force was observed.

Film Heat Seal Strength

In this disclosure, the “Heat Seal Strength Test” was performed asfollows. ASTM conditions were employed. Heat seal data was generatedusing a conventional Instron Tensile Tester. In this test, two filmsamples are sealed over a range of temperatures (the two film sampleswere cut from the same roll of 2.0 mil (51-μm) thick film). Thefollowing parameters were used in the Heat Seal Strength Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 40 psi (0.28 N/mm²); temperature range, 212° F. to302° F. (100° C. to 150° C.) and temperature increment, 9° F. (5° C.).After aging for at least 24 hours at ASTM conditions, seal strength wasdetermined using the following tensile parameters: pull (crosshead)speed, 12 inch/min (2.54 cm/min); direction of pull, 90° to seal, and; 5samples of film were tested at each temperature increment. The SealInitiation Temperature, hereinafter S.I.T., is defined as thetemperature required to form a commercially viable seal; a commerciallyviable seal has a seal strength of 2.0 lb per inch of seal (8.8 N per25.4 mm of seal).

Film Hexane Extractables

Hexane extractables was determined according to the Code of FederalRegistration 21 CFR § 177.1520 Para (c) 3.1 and 3.2; wherein thequantity of hexane extractable material in a film is determinedgravimetrically. Elaborating, 2.5 grams of 3.5 mil (89 μm) monolayerfilm was placed in a stainless steel basket, the film and basket wereweighed (w^(i)). While in the basket the film was: extracted withn-hexane at 49.5° C. for two hours; dried at 80° C. in a vacuum oven for2 hours; cooled in a desiccator for 30 minutes, and; weighed (w^(f)).The percent loss in weight is the percent hexane extractables (w^(C6)):w^(C6)=100×(w^(i)−w^(f))/w^(i).

EXAMPLES

Pilot Plant Polymerizations

The following examples are presented for the purpose of illustratingselected embodiments of this disclosure, it being understood that, theexamples presented hereinafter do not limit the claims presented.

Disclosed embodiments of the ethylene interpolymer products wereprepared in a continuous solution pilot plant operated in both seriesmode and parallel mode as fully described below. Comparative ethyleneinterpolymer products were also prepared in the same pilot plant.

Series Polymerization

Series mode Example 50 and Example 51 of ethylene interpolymer productsand series mode Comparative 60, shown in Tables 4A through 4C, wereproduced using an R1 pressure from about 14 MPa to about 18 MPa; R2 wasoperated at a lower pressure to facilitate continuous flow from R1 toR2. In series mode the first exit stream from R1 flows directly into R2.Both CSTR's were agitated to give conditions in which the reactorcontents were well mixed. The process was operated continuously byfeeding fresh process solvent, ethylene, 1-octene and hydrogen to thereactors. Methylpentane was used as the process solvent (a commercialblend of methylpentane isomers). The volume of the first CSTR reactor(R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2)was 5.8 gallons (22 L) and the volume of the tubular reactor (R3) was0.58 gallons (2.2 L).

The following components were used to prepare the first homogeneouscatalyst formulation that was injected into R1, i.e. the bridgedmetallocene catalyst formulation comprising: a component A, eitherdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂] (abbreviated CpF-1) ordiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl, [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] (abbreviated CpF-2); component M,methylaluminoxane (MMAO-07); component B, trityltetrakis(pentafluoro-phenyl)borate, and; component P,2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, CpF-1 was used toproduce Example 50 and CpF-2 was used to produce Examples 51 and 52. Toprepare the bridged metallocene catalyst formulation the followingcatalyst component solvents were used: methylpentane for components Mand P, and; xylene for component A and B.

Comparative ethylene interpolymer products were prepare by injecting thethird homogeneous catalyst formulation into R1. In Comparative ethyleneinterpolymer products the third homogeneous catalyst formulationreplaces the first homogeneous catalyst formulation. One embodiment ofthe third homogeneous catalyst formulation was an unbridged single sitecatalyst formulation comprising: component C, either cyclopentadienyltri(tertiary butyl)phosphinimine titanium dichloride[Cp[(t-Bu)₃PN]TiCl₂] (abbreviated PIC-1) or cyclopentadienyltri(isopropyl)phosphinimine titanium dichloride[Cp[(isopropyl)₃PN]TiCl₂] (abbreviated PIC-2); component M,methylaluminoxane (MMAO-07); component B, trityltetrakis(pentafluoro-phenyl)borate, and; component P,2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, PIC-2 was used toproduce Comparative 60 and PIC-1 was used to produce Comparative 61. Toprepare the unbridged single site catalyst formulation the followingcatalyst component solvents were used: methylpentane for components Mand P, and; xylene for component A and B.

The quantity of CpF-1 or CpF-2 added to reactor 1 (R1) is shown in Table4A, e.g. “R1 catalyst (ppm)” was 0.72 ppm of CpF-1 in the case ofExample 50. The efficiency of the first homogeneous catalyst formulationwas optimized by adjusting the mole ratios of the catalyst componentsand the R1 catalyst inlet temperature. As shown in Table 4A, the moleratios optimized were: ([M]/[A]), i.e. [(MMAO-07)/(CpF-1)]; ([P]/]M]),i.e. [(2,6-di-tert-butyl-4-ethylphenol)/(MMAO-07)], and; ([B]/[A]), i.e.[(trityl tetrakis(pentafluoro-phenyl)borate)/(CpF−1)]. To be more clear,in Example 50 (Table 4A), the mole ratios in R1 were: ([M]/[A])=122;([P]/[M])=0.40, and; ([B]/[A])=1.47. As shown in Table 4C, the catalystinlet temperature of the bridged metallocene catalyst formulation was:about 145° C. in the case of CpF-1, and; about 21 to about 25° C. in thecase of CpF-2.

In the Comparatives the quantity of PIC-1 or PIC-2 added to reactor 1(R1) is shown in Table 4A, e.g. “R1 catalyst (ppm)” was 0.14 ppm ofPIC-2 in the case of Comparative 60. The efficiency of the thirdhomogeneous catalyst formulation was optimized by adjusting the moleratios of the catalyst components and the R1 catalyst inlet temperature.As shown in Table 4A, the mole ratios optimized were: ([M]/[C]), i.e.(MMAO-07)/(PIC-2); ([P]/[M]), i.e.(2,6-di-tert-butyl-4-ethylphenol)/(MMAO-07), and; ([B]/[C]), i.e.(trityl tetrakis(pentafluoro-phenyl)borate)/(PIC-2). To be more clear,as shown in Table 4A, in Comparative 60 the mole ratios in R1 were:([M]/[C])=65; ([P]/[M])=0.30, and; ([B]/[C])=1.20. As shown in Table 4C,the R1 catalyst inlet temperature of the unbridged single site catalystformulation was about 30 to about 32° C.

In both Examples and Comparatives a second homogeneous catalystformulation was injected into the second reactor (R2), e.g. an unbridgedsingle site catalyst formulation, PIC-1 or PIC-2 as specified in Table4A.

Average residence time of the solvent in a reactor is primarilyinfluenced by the amount of solvent flowing through each reactor and thetotal amount of solvent flowing through the solution process, thefollowing are representative or typical values for the Examples andComparatives shown in Tables 4A-4C, as well as Examples shown in Tables6A-6C: average reactor residence times were: about 61 seconds in R1,about 73 seconds in R2, about 7.3 seconds for an R3 volume of 0.58gallons (2.2 L).

Polymerization in the continuous solution polymerization process wasterminated by adding a catalyst deactivator to the third exit streamexiting the tubular reactor (R3). The catalyst deactivator used wasoctanoic acid (caprylic acid), commercially available from P&GChemicals, Cincinnati, Ohio, U.S.A. The catalyst deactivator was addedsuch that the moles of fatty acid added were 50% of the total molaramount of hafnium, titanium and aluminum added to the polymerizationprocess; to be clear, the moles of octanoic acid added=0.5×(moleshafnium+moles titanium+moles aluminum); this mole ratio was consistentlyused in both Examples and Comparatives.

A two-stage devolitizing process was employed to recover the ethyleneinterpolymer product from the process solvent, i.e. two vapor/liquidseparators were used and the second bottom stream (from the second V/Lseparator) was passed through a gear pump/pelletizer combination.

Prior to pelletization the ethylene interpolymer product was stabilizedby adding 500 ppm of Irganox 1076 (a primary antioxidant) and 500 ppm ofIrgafos 168 (a secondary antioxidant), based on weight of the ethyleneinterpolymer product. Antioxidants were dissolved in process solvent andadded between the first and second V/L separators.

Tables 4A-4C disclose additional process parameters, e.g. ethylene and1-octene splits between the reactors, and reactor temperatures andethylene conversions, etc. In Tables 4A-4C the targeted ethyleneinterpolymer product was about 1.0 dg/min (melt index (I₂), as measuredaccording to ASTM D1239, 2.16 kg load, 190° C.) and about 0.917 g/cm³(as measured according to ASTM D792).

Tables 6A-6C disclose continuous solution process parameters for Example58 (about 4 dg/min (I₂) and about 0.928 g/cc) and Example 59 (about 0.24dg/min (I₂) and about 0.944 g/cc).

Parallel Polymerization

The pilot plant described above was reconfigured to operate in parallelmode. In parallel mode the first exit stream (exiting the first reactor)by-passes the second reactor and the first exit stream is combined withthe second exit stream (exiting the second reactor) downstream of thesecond reactor. To be more clear, FIG. 2 illustrates parallel modeoperation where: the first exit stream 11 g (dotted line) by-passes thesecond reactor 12 a, streams 11 g and stream 12 c (second exit streamfrom reactor 12 a) are combined to form a third exit stream 12 d, and;the third exit stream flows into the tubular reactor 17. As shown inTables 4A through 4C, Example 52 is one embodiment of an ethyleneinterpolymer product synthesized using parallel mode operation. Catalystoptimization and additional process parameters for Example 52, e.g.ethylene and 1-octene splits between the reactors, and reactortemperatures and ethylene conversions, etc., are summarized in Tables4A-4C.

Given the continuous solution polymerization conditions shown in Table4A through Table 4C, the physical properties of the resulting ethyleneinterpolymer products are summarized in Table 5, i.e. Examples 50-52.Table 5 also discloses the physical properties of Comparatives 60, 61and 67. Comparative 67 was a commercially available solution processethylene/1-octene polymers produced by NOVA Chemicals Company (Calgary,Alberta, Canada) SURPASS® FPs117-C, produced using the unbridged singlesite catalyst formulation in reactors 1 and 2. As shown in Table 5,Neutron Activation Analysis results disclose catalyst residues inExamples 51 and 52 and Comparatives 60, 61 and 67. Given the continuoussolution polymerization conditions shown in Tables 6A through 6C, theresulting ethylene interpolymer products produced are summarized inTable 7, i.e. Examples 58 and 59.

Table 8 compares physical attributes of Example 51 with Comparative 67,i.e. the weight fractions, molecular weights (M_(n), M_(w) andM_(w)/M_(n)), branching (#C6/1000 C), CDBI₅₀, density, melt index andlong chain branching factor (LDBF) of the first ethylene interpolymer,second ethylene interpolymer, third ethylene interpolymer and theethylene interpolymer product are disclosed. Results in Table 8 weregenerated by deconvoluting the SEC and CTREF curves of Example 51 andComparative 67 into their respective components. Graphically, FIG. 4illustrates the deconvolution of the experimentally measured SEC ofExample 51 into three components, i.e. the first, second and thirdethylene interpolymer. In Example 51 the first ethylene interpolymerhaving a density of 0.8940 g/cm³ was produced using an((1-octene)/(ethylene))^(R1) weight ratio of 0.41. In contrast, inComparative 67 the first ethylene interpolymer density having a densityof 0.9141 g/cm³ was produced using an ((1-octene)/(ethylene))^(R1)weight ratio of 1.43. Even though Example 51 was produced with a 71%lower octene/ethylene ratio, relative to Comparative 67, the firstethylene interpolymer in Example 51 was of lower density. Both of thesetrends shown by Example 51 employing the bridged metallocene catalystformulation, i.e. a lower (octene/ethylene) ratio and a lower densityare advantageous, relative to Comparative 67 employing the unbridgedsingle site catalyst formulation. Table 8 also discloses a Δρ, (ρ²−ρ¹)or [(the density of the second ethylene interpolymer)−(the density ofthe first ethylene interpolymer)], was higher in Example 51 relative toComparative 67. Specifically, Δρ was 0.0473 and 0.0040 g/cm³ for Example51 and Comparative 67, respectively. Higher Δρ's are advantageous inseveral end-use applications. In FIG. 4: the molecular weightdistribution of the first, second and third ethylene interpolymers wereassumed similar to Flory distributions. The weight percent of the thirdethylene interpolymer was assumed to be 5%.

As shown in Table 8, the weight average molecular weights (M_(w)) of thefirst ethylene interpolymers in Example 51 and Comparative 67 were141,247 and 165,552, respectively. The lower M_(w) of the first ethyleneinterpolymer in Example 51 reflects the fact that reactor 1 contained5.35 ppm of hydrogen; in contrast, in Comparative 67 the first ethyleneinterpolymer was synthesized using 0.60 ppm of hydrogen in reactor 1.Those of ordinary experience are cognizant of the fact that hydrogen isused to control M_(w) (or melt index) in olefin polymerization, i.e.hydrogen is very effective in terminating propagating macromolecules.Further, given Table 8, those of ordinary experience would haverecognized the higher molecular weight capability of the bridgedmetallocene catalyst relative to the unbridged single site catalyst.Elaborating, relative to Comparative 67, the amount of hydrogen used tosynthesize the first ethylene interpolymer in Example 51 was about anorder of magnitude higher, and yet the M_(w)'s differed by only 15%.This trend of higher hydrogen concentration for the bridged metallocenecatalyst formulation, relative to the unbridged single site catalystformulation, demonstrated the higher molecular weight capability of theformer. Example 51 and Comparative 67 were produced at similar reactortemperatures, i.e. 139.5° C. and 140.0° C., respectively.

Blown Films: Ethylene Interpolymer Products

Monolayer blown films were produced on a Gloucester extruder, 2.5 inch(6.45 cm) barrel diameter, 24/1 L/D (barrel Length/barrel Diameter)equipped with: a barrier screw; a low pressure 4 inch (10.16 cm)diameter die with a 35 mil (0.089 cm) die gap, and; a Western PolymerAir ring. Blown films, 1.0 mil (25 μm) thick, were produced at aconstant output rate of 100 lb/hr (45.4 kg/hr) by adjusting extruderscrew speed, and; the frost line height was maintained at about 16 inch(40.64 cm) by adjusting the cooling air. Blown film processingconditions for Examples 51 and 52 and Comparative 67 are disclosed inTable 9. Monolayer blown film was also produced at 2.0 mil (51 μm) and3.5 mil (89 μm) to determine the seal initiation temperature (SIT) andhexane extractables, respectively. Processing aid, encapsulated in apolyethylene masterbatch, was added to all resins prior to filmextrusion; the processing aid added was Dynamar FX 5920A (commerciallyavailable from The 3M Company, St. Paul, Minn., USA).

As shown in Table 9, in blown film processes, Examples 51 and 52 haveimproved processability relative to Comparative 67, i.e. lower extrusionpressures and lower extruder current draw. Improved processability isdesirable to the film converter because improved processability meanshigher production rates, e.g. an increase in the pounds of film producedper hour, or feet (meters) of film produced per hour.

As shown in Table 10A, relative to Comparative 67, blown films producedfrom Examples 51 and 52 can be advantageously used in any filmapplication where improved film hexane extractables are desired, e.g. infood packaging applications. The hexane extractables of a blown film,Example 51F, prepared from Example 51 were: 65% lower relative toComparative 67. The hexane extractables of a blown film, Example 52F,prepared from Example 52 were: 54% lower relative to Comparative 67.

As shown in Table 10A, the seal initiation temperature (SIT) of Example51F film (produced in a series solution process) was 93.6° C.; which wasimproved (i.e. lower by 6%) relative to Comparative 67's SIT of 99.1° C.The seal initiation temperature (SIT) of Example 52F film (produced in aparallel solution process) was 89.1° C.; which was improved (i.e. lowerby 10%) relative to Comparative 67's SIT of 99.1° C. As shown in Table10A, the Tack Onset (at 1.0N) of film Examples 51F and 52F were 90 and86° C., respectively; which were improved (i.e. lower by 11% and 15%,respectively) relative to film Comparative 67F's SIT of 101° C. As shownin Table 10A, the temperature at which the maximum Hot Tack was observedwas 105 and 100° C. for film Examples 51F and 52F, respectively, whichcan be compared to Comparative 67F's 115° C. value. To be clear, thetemperature at maximum Hot Tack of film 51F was improved (lower) by 9%,relative to Comparative 67F; similarly the temperature at maximum HotTack of film 52F was improved by 13%, relative to Comparative 67F. LowerSIT's, lower Tack onset and a lower temperature at maximum Hot Tack aredesirable in food packaging applications, e.g. high speed verticalform-fill-seal food packaging lines.

As shown in Table 10A, the machine direction Elmendorf tear strength offilm Example 52F was 288 g was similar to film Comparative 67F machinedirection Elmendorf tear strength of 282 g. The transverse directionElmendorf tear strength of film Example 52F was 568 g; i.e. improved(higher by 12%) relative to film Comparative 67F transverse directionElmendorf film tear strengths of 507 g. The dart impact of Example 51F(series configuration) was 800 g, i.e. improved by 100% relative toComparative 67F dart impact of 400 g.

As shown in Table 10B, relative to Comparative 67F, blown films producedfrom Examples 51F and 52F can be advantageously used in film applicationwhere higher film moduli are desired. One of the desirable features ofhigher film moduli is the ability to reduce film thickness, reducingfilm thickness contributes to source reduction, sustainability andreduces overall costs. The machine direction 1% secant modulus ofExample 51F (212 MPa) was 29% improved (higher) relative to Comparative67F (164 MPa), and; the transverse direction 1% secant modulus ofExample 51F (255 MPa) was 58% improved relative to Comparative 67F (161MPa). The machine direction 1% secant modulus of Example 52F (228 MPa)was 39% improved (higher) relative to Comparative 67F, and; thetransverse direction 1% secant modulus of Example 52F (258 MPa) was 60%improved relative to Comparative 67F. This same trend was also evidentin the 2% secant modulus. Specifically, the machine direction 2% secantmodulus of Example 51F (178 MPa) was 25% improved (higher) relative toComparative 67F (142 MPa), and; the transverse direction 2% secantmodulus of Example 51F (211 MPa) was 54% improved relative toComparative 67F (137 MPa). Similarly, the machine direction 2% secantmodulus of Example 52F (190 MPa) as 33% improved (higher) relative toComparative 67F, and; the transverse direction 2% secant modulus ofExample 52F (215 MPa) was 57% improved relative to Comparative 67F.Table 10B also shows improved (higher) tensile yield strength forExamples 51F and 52F, relative to Comparative 67F. Higher yieldstrengths reduce the tendency of a loaded package to yielding, deform ordistort under its own weight. The machine direction tensile yieldstrength of Example 51F was 10.2 MPa, which was 12% improved (higher)relative to Comparative 67F (9.1 MPa), and; the transverse directiontensile yield strength of Example 51F (11.4 MPa) was 31% improvedrelative to Comparative 67F (8.7 MPa). The machine direction tensileyield strength of Example 52F was 10.5 MPa, which was 15% improved(higher) relative to Comparative 67F, and; the transverse directiontensile yield strength of Example 52F (11.5 MPa) was 32% improvedrelative to Comparative 67F.

As shown in Table 10B, the blown film produced from Example 52 (parallelmode) had a higher (21% improved) film toughness (Total Energy to BreakTD) of 1605 ft·lb/in³, relative to the blown film produced fromComparative 67 (series mode) having a film toughness of 1327 ft·lb/in³.

Continuous Polymerization Unit (CPU)

Comparison of Catalyst Formulations in One Reactor

Small scale continuous solution polymerizations were conducted on aContinuous Polymerization Unit, hereinafter CPU. The purpose of theseexperiments were to directly compare the performance of the bridgedmetallocene catalyst formulation (containing component A, CpF-1) withthe unbridged single site catalyst formulation (containing component C,PIC-1) in one reactor.

The single reactor of the CPU was a 71.5 mL continuously stirred CSTR,polymerizations were conducted at 130° C., 160° C. or 190° C. and thereactor pressure was about 10.5 MPa. The CPU included a 20 mL upstreammixing chamber that was operated at a temperature that was 5° C. lowerthan the downstream polymerization reactor. The upstream mixing chamberwas used to pre-heat the ethylene, optional α-olefin and a portion ofthe process solvent. Catalyst feeds and the remaining solvent were addeddirectly to the polymerization reactor as a continuous process. Thetotal flow rate to the polymerization reactor was held constant at 27mL/minute. The components of the bridged metallocene catalystformulation (component A, component M, component B and component P) wereadded directly to the polymerization reactor to maintain the continuouspolymerization process. More specifically: component A and component Bwere premixed in xylene and injected directly into the reactor, and;component M and optionally component P were premixed in process solventand injected directly into the reactor. In the comparative experiments,the components of the unbridged single site catalyst formulation(component C, component M, component B and component P) were addeddirectly to the polymerization reactor to maintain the continuouspolymerization process. More specifically: component C and component Bwere premixed in xylene and injected directly into the reactor, and;component M and optionally component P were premixed in process solventand injected directly into the reactor. In the examples, the component Aemployed was CpF-1 [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]. In the comparatives,the component C employed was PIC-1 ([Cp[(t-Bu)₃PN]TiCl₂]). Components M,B and P were methylaluminoxane (MMAO-07), trityltetrakis(pentafluoro-phenyl)borate, and 2,6-di-tert-butyl-4-ethylphenol,respectively. Upon injection, the catalyst was activated in situ (in thepolymerization reactor) in the presence of ethylene and optionalα-olefin comonomer. Component M was added such that the mole ratio of([M]/[A]) or ([M]/[C]) was about 80; component B was added such that themole ratio of ([M]/[A]) or ([M]/[C]) was about 1.0, and; component P wasadded such that the mole ratio of ([P]/[M]) was about 0.4.

Ethylene was supplied to the reactor by a calibrated thermal mass flowmeter and was dissolved in the reaction solvent prior to thepolymerization reactor. Optional comonomer (1-octene) was premixed withethylene before entering the polymerization reactor, the(1-octene)/(ethylene) weight ratio varied from 0 to about 6.0. Ethylenewas fed to the reactor such that the ethylene concentration in thereactor varied from about 7 to about 15 weight %; where weight % is theweight of ethylene divided by the total weight of the reactor contents.The internal reaction temperature was monitored by a thermocouple in thepolymerization medium and was controlled at the target set point to±0.5° C. Solvent, monomer, and comonomer streams were all purified bythe CPU systems prior to entering the reactor.

The ethylene conversion, Q^(CPU), i.e. the fraction of ethyleneconverted was determined by an online gas chromatograph (GC) andpolymerization activity, K_(p) ^(CPU), having dimensions of[L/(mmol·min)] was defined as:

$K_{p}^{CPU} = {Q^{CPU}\left( \frac{1 - Q^{CPU}}{\lbrack{catalyst}\rbrack \times {HUT}^{CPU}} \right)}$where HUT^(CPU) was a reciprocal space velocity (Hold Up Time) in thepolymerization reactor having dimensions of minutes (min), and;[catalyst] was the concentration of catalyst in the polymerizationreactor expressed in mmol/L of titanium or hafnium. In some CPUexperiments, Q^(CPU) was held constant at about 90% and the HUT^(CPU)was held constant at about 2.5 minutes. In other CPU experiments,Q^(CPU) was varied from about 75 to about 95%. Downstream of the reactorthe pressure was reduced to atmospheric pressure. The polymer productwas recovered as a slurry in the process solvent and subsequently driedby evaporation in a vacuum oven prior to characterization.

At a polymerization temperature of 130° C., the CPU conditions wereadjusted to synthesize ethylene interpolymers at approximately constantmelt index and density; specifically, a first ethylene interpolymersynthesized with the bridged metallocene catalyst formulation and acomparative ethylene interpolymer produced with the unbridged singlesite catalyst formulation. As shown by each row in Table 11A, at areactor temperature of 130° C., the bridged metallocene catalystformulation produced an improved (higher) SEC weight average molecularweight (M_(w) ^(A)), relative to the comparative unbridged single sitecatalyst formulation (M_(w) ^(C)). The percent improvement in M_(w) wasat least 5% as calculated using the following formula:% Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)Similarly, at a polymerization temperature of 160° C., each row of Table11B shows that the bridged metallocene catalyst formulation produced animproved (higher) SEC weight average molecular weight (M_(w) ^(A)),relative to the comparative unbridged single site catalyst formulation(M_(w) ^(C)). The percent improvement in M_(w) was at least 10%.

As shown in Table 12A, at a polymerization temperature of 130° C., the(α-olefin/ethylene) weight ratio in the reactor had to be adjusted suchthat ethylene interpolymers were produced having a target density. Morespecifically, (α-olefin/ethylene)^(A) was required to synthesize a firstethylene interpolymer, having a target density, using the bridgedmetallocene catalyst formulation. In contrast, (α-olefin/ethylene)^(C)was required to synthesize a control ethylene interpolymer, having thetarget density, using the unbridged single site catalyst formulation. Asshown by each row in Table 12A, at 130° C., the bridged metallocenecatalyst formulation allows the operation of the continuous solutionpolymerization process at an improved (reduced) (α-olefin/ethylene)weight ratio, relative to the control unbridged single site catalystformulation. The percent reduction in (α-olefin/ethylene) weight ratiowas at least −70% as calculated using the following formula:

${\%\mspace{14mu}{{Reduced}\left\lbrack \frac{\alpha\text{-}{olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$

Similarly, at a polymerization temperature of 160° C., each row of Table12B shows that the bridged metallocene catalyst formulation allows theoperation of the continuous solution polymerization process at animproved (reduced) (α-olefin/ethylene) weight ratio, relative to thecontrol unbridged single site catalyst formulation. In Table 12B, thepercent reduction in (α-olefin/ethylene) weight ratio was at least −70%.

CPU experiments were also conducted to collect samples of the firstethylene interpolymer produced with the bridged metallocene catalystformulation for ¹³C NMR characterization to quantify the amount of longchain branching (LCB). Table 13 summarizes typical CPU processconditions at three reactor temperatures (130, 160 and 190° C.) and twolevels of ethylene conversion (about 75 wt % and about 95 wt %). Polymercharacterization data (of the first ethylene interpolymer produced withthe bridged metallocene catalyst formulation) is summarized in Table 14,the level of long chain branching in the ethylene interpolymers producedwith the bridged metallocene catalyst formulation varied from 0.03 to0.23 long chain branches (LCB) per 1000 carbon atoms.

TABLE 1A Reference resins (linear ethylene polymers) containingundetectable levels of Long Chain Branching (LCB). SCBD Reference Mv [η]CH₃#/ ZSV Resins (g/mole) (dL/g) M_(w)/M_(n) A 1000 C (poise) Resin 11.06E+05 1.672 2.14 1.9772 10.5 7.81E+04 Resin 2 1.11E+05 1.687 2.001.9772 11.2 7.94E+04 Resin 3 1.06E+05 1.603 1.94 1.9772 15.9 7.28E+04Resin 4 1.07E+05 1.681 1.91 1.9772 11.0 8.23E+04 Resin 5 7.00E+04 1.1922.11 1.9772 13.7 1.66E+04 Resin 6 9.59E+04 1.497 1.88 1.9772 12.65.73E+04 Resin 7 1.04E+05 1.592 1.85 1.9772 12.8 6.60E+04 Resin 85.09E+04 0.981 2.72 2.1626 0.0 6.42E+03 Resin 9 5.27E+04 0.964 2.812.1626 0.0 6.42E+03 Resin 10 1.06E+05 1.663 1.89 1.1398 13.3 7.69E+04Resin 11 1.10E+05 1.669 1.81 1.1398 19.3 7.31E+04 Resin 12 1.07E+051.606 1.80 1.1398 27.8 6.99E+04 Resin 13 6.66E+04 1.113 1.68 2.1626 17.81.39E+04 Resin 14 6.62E+04 1.092 1.76 2.1626 21.4 1.45E+04 Resin 156.83E+04 1.085 1.70 2.1626 25.3 1.44E+04 Resin 16 7.66E+04 1.362 2.512.1626 4.0 3.24E+04 Resin 17 6.96E+04 1.166 2.53 2.1626 13.9 2.09E+04Resin 18 6.66E+04 1.134 2.54 2.1626 13.8 1.86E+04 Resin 19 5.81E+041.079 2.44 2.1626 5.8 1.10E+04 Resin 20 7.85E+04 1.369 2.32 2.1626 3.73.34E+04 Resin 21 6.31E+04 1.181 2.26 2.1626 4.3 1.61E+04 Resin 227.08E+04 1.277 2.53 2.1626 3.6 2.58E+04 Resin 23 9.91E+04 1.539 3.092.1626 14.0 8.94E+04 Resin 24 1.16E+05 1.668 3.19 2.1626 13.3 1.32E+05Resin 25 1.12E+05 1.689 2.71 2.1626 12.8 1.38E+05 Resin 26 1.14E+051.690 3.37 2.1626 8.0 1.48E+05 Resin 27 9.55E+04 1.495 3.44 2.1626 13.88.91E+04 Resin 28 1.00E+05 1.547 3.33 2.1626 14.1 9.61E+04 Resin 291.07E+05 1.565 3.52 2.1626 13.0 1.12E+05 Resin 30 1.04E+05 1.525 3.732.1626 13.4 1.10E+05 Resin 31 1.10E+05 1.669 3.38 2.1626 8.7 1.26E+05Resin 32 1.09E+05 1.539 3.42 2.1626 13.4 1.07E+05 Resin 33 8.04E+041.474 5.29 2.1626 1.7 7.60E+04 Resin 34 8.12E+04 1.410 7.64 2.1626 0.99.11E+04 Resin 35 7.56E+04 1.349 9.23 2.1626 1.0 9.62E+04 Resin 367.34E+04 1.339 8.95 2.1626 1.1 1.00E+05 Resin 37 1.01E+05 1.527 3.762.1626 13.3 1.11E+05

TABLE 1B Long Chain Branching Factor (LCBF) of reference resins (linearethylene polymers) containing undetectable levels of Long ChainBranching (LCB). Reference Log ZSV_(c) Log IV_(c) S_(h) S_(v) LCBFResins (log(poise)) log (dL/g) (dimensionless) (dimensionless)(dimensionless) Resin 1 4.87E+00 2.46E−01 −5.77E−02 −1.21E−02 3.49E−04Resin 2 4.90E+00 2.52E−01 −5.39E−02 −1.13E−02 3.05E−04 Resin 3 4.87E+002.41E−01 −2.46E−02 −5.16E−03 6.33E−05 Resin 4 4.93E+00 2.50E−01−9.46E−03 −1.99E−03 9.41E−06 Resin 5 4.20E+00 1.07E−01 −6.37E−02−1.34E−02 4.26E−04 Resin 6 4.78E+00 2.04E−01 5.83E−02 1.22E−02 3.57E−04Resin 7 4.85E+00 2.31E−01 −1.73E−03 −3.65E−04 3.16E−07 Resin 8 3.69E+00−8.43E−03 −2.17E−02 −4.55E−03 4.93E−05 Resin 9 3.68E+00 −1.58E−021.21E−04 2.44E−05 1.47E−09 Resin 10 4.91E+00 2.38E−01 2.19E−02 4.60E−035.04E−05 Resin 11 4.90E+00 2.48E−01 −2.96E−02 −6.21E−03 9.17E−05 Resin12 4.88E+00 2.42E−01 −1.99E−02 −4.19E−03 4.17E−05 Resin 13 4.21E+009.14E−02 2.36E−02 4.96E−03 5.86E−05 Resin 14 4.21E+00 9.22E−02 1.89E−023.97E−03 3.75E−05 Resin 15 4.22E+00 1.00E−01 −9.82E−03 −2.06E−031.01E−05 Resin 16 4.42E+00 1.44E−01 −1.23E−02 −2.59E−03 1.60E−05 Resin17 4.23E+00 1.01E−01 −4.64E−03 −9.75E−04 2.26E−06 Resin 18 4.18E+008.91E−02 1.66E−03 3.47E−04 2.87E−07 Resin 19 3.97E+00 4.73E−02 −1.09E−02−2.29E−03 1.25E−05 Resin 20 4.47E+00 1.45E−01 2.28E−02 4.78E−03 5.44E−05Resin 21 4.16E+00 8.23E−02 1.78E−02 3.73E−03 3.31E−05 Resin 22 4.32E+001.15E−01 2.45E−02 5.14E−03 6.30E−05 Resin 23 4.78E+00 2.22E−01 −2.25E−02−4.73E−03 5.31E−05 Resin 24 4.94E+00 2.56E−01 −3.13E−02 −6.57E−031.03E−04 Resin 25 5.02E+00 2.59E−01 3.91E−02 8.21E−03 1.60E−04 Resin 264.97E+00 2.48E−01 3.94E−02 8.27E−03 1.63E−04 Resin 27 4.74E+00 2.09E−01−2.83E−03 −5.95E−04 8.42E−07 Resin 28 4.79E+00 2.24E−01 −3.13E−02−6.57E−03 1.03E−04 Resin 29 4.83E+00 2.28E−01 −2.96E−03 −6.22E−049.20E−07 Resin 30 4.80E+00 2.18E−01 1.47E−02 3.08E−03 2.26E−05 Resin 314.90E+00 2.44E−01 −1.40E−02 −2.94E−03 2.06E−05 Resin 32 4.82E+002.23E−01 1.27E−02 2.66E−03 1.69E−05 Resin 33 4.51E+00 1.72E−01 −6.37E−02−1.34E−02 4.26E−04 Resin 34 4.45E+00 1.52E−01 −2.68E−02 −5.62E−037.52E−05 Resin 35 4.40E+00 1.33E−01 1.55E−02 3.26E−03 2.53E−05 Resin 364.43E+00 1.30E−01 5.82E−02 1.22E−02 3.55E−04 Resin 37 4.80E+00 2.17E−011.77E−02 3.71E−03 3.28E−05

TABLE 2 Long Chain Branching Factor (LCBF) of ethylene interpolymerproduct Examples 50-52 and 58 and Comparatives 60, 61 and 67. Example 50Example 51 Example 52 Example 58 Comp. 60 Comp. 61 Comp. 67 Mv 1.05E+059.09E+04 9.07E+04 5.96E+04 n/a 1.00E+05 9.42E+04 (g/mole) [η] 1.4961.314 1.340 0.945 n/a 1.538 1.474 (dL/g) Mw/Mn 2.86 2.65 2.04 6.23 2.882.37 3.08 A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB 16.115.8 16.2 12.6 13.5 12.1 14.6 (CH₃#/1000 C) ZSV 1.61E+05 1.65E+051.77E+05 7.33E+04 1.05E+05 8.06E+04 8.98E+04 (poise) Log ZSV_(c)5.07E+00 5.11E+00 5.24E+00 4.43E+00 4.88E+00 4.84E+00 4.79E+00(log(poise)) Log IVc 2.17E−01 1.61E−01 1.70E−01 1.01E−02 n/a 2.17E−012.05E−01 (log(dL/g)) S_(h) 2.84E−01 5.93E−01 6.79E−01 6.30E−01 n/a5.60E−02 6.17E−02 (dimensionless) S_(v) 5.96E−02 1.24E−01 1.43E−011.32E−01 n/a 1.18E−02 1.30E−02 (dimensionless) LCBF 8.45E−03 3.68E−024.84E−02 4.17E−02 n/a 3.30E−04 4.00E−04 (dimensionless)

TABLE 3 Long Chain Branching Factor (LCBF) of Comparative ethylenepolymers: Comparatives A-C and Comparatives D-G. Comp. A Comp. B Comp. CComp. D Comp. E Comp. F Comp. G Mv 8.79E+04 8.94E+04 8.70E+04 9.75E+041.02E+05 1.04E+05 9.76E+04 (g/mole) [η] 1.300 1.314 1.293 1.441 1.4881.507 1.448 (dL/g) Mw/Mn 1.88 1.80 1.89 3.04 2.85 2.79 2.89 A 2.16262.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB 23.2 23.3 23.4 14.2 13.714.1 15.1 (CH₃#/1000 C) ZSV 1.51E+05 1.51E+05 1.53E+05 1.56E+05 1.43E+051.55E+05 1.35E+05 (poise) Log ZSV_(c) 5.20E+00 5.22E+00 5.21E+005.03E+00 5.02E+00 5.06E+00 4.99E+00 (log(poise)) Log IVc 1.74E−011.79E−01 1.72E−01 1.95E−01 2.08E−01 2.15E−01 2.00E−01 (log(dL/g)) S_(h)6.22E−01 6.14E−01 6.35E−01 3.51E−01 2.76E−01 2.90E−01 2.87E−01(dimensionless) S_(v) 1.31E−01 1.29E−01 1.33E−01 7.38E−02 5.81E−026.09E−02 6.03E−02 (dimensionless) LCBF 4.06E−02 3.96E−02 4.23E−021.30E−02 8.03E−03 8.83E−03 8.65E−03 (dimensionless) Ti (ppm) 0.33 ±0.01^(a) 1.5 2.2 2.2 2.0 Hf (ppm) ^(b) ^(b) ^(b) ^(b) ^(b) Internal0.006 0.006 0.006 0.004 0.004 0.004 0.004 Unsaturations/ 100 C SideChain 0.001 0.025 0.025 0.002 0.003 0.002 0.004 Unsaturations/ 100 CTerminal 0.008 0.007 0.007 0.025 0.020 0.021 0.03 Unsaturations/ 100 C^(a)average of AFFINITY (3 samples, but not Comp. A-C); via NeutronActivation Analysis (N.A.A.) ^(b) undetectable via Neutron ActivationAnalysis

TABLE 4A Continuous solution process catalyst parameters for Examples 50through 52 and Comparatives 60 and 61 Process Parameter Example 50Example 51 Example 52 Comp. 60 Comp. 61 Reactor Mode Series SeriesParallel Series Parallel R1 Catalyst^(a) CpF-1 CpF-2 CpF-2 PIC-2 PIC-1(component A, or component C) R2 Catalyst^(b) PIC-1 PIC-1 PIC-1 PIC-2PIC-1 R1 catalyst (ppm) 0.72 0.40 0.44 0.14 0.26 R1 ([M^(c)]/[A]) or 12245 45 100 65 R1 ([M]/[C]) mole ratio R1 ([P^(d)]/[M]) mole ratio 0.400.15 0.15 0.5 0.30 R1 ([B^(e)]/[A]) or 1.47 1.21 1.21 1.2 1.20 R1([B]/[C]) mole ratio R2 catalyst (ppm) 0.15 0.17 0.59 0.38 0.27 R2([M^(c)]/[C]) mole ratio 25 25 65 30 65 R2 ([P^(d)]/[M]) mole ratio 0.300.30 0.30 0.5 0.30 R2 ([B^(e)]/[C]) mole ratio 1.50 1.50 1.50 1.5 1.50Prod. Rate (kg/h) 64.1 64.4 60.2 76.7 49.5 ^(a)Catalysts: CpF-1 =[(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]: CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂];PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂], and; PIC-2 = [Cp[(isopropyl)₃PN]TiCl₂].^(b)in-line Ziegler-Natta catalyst formulation ^(c)methylaluminoxane(MMAO-7) ^(d)2,6-di-tert-butyl-4-ethylphenol ^(e)trityltetrakis(pentafluoro-phenyl)borate

TABLE 4B Continuous solution process catalyst parameters for Examples 50through 52 and Comparatives 60 and 61. Process Parameter Example 50Example 51 Example 52 Comp. 60 Comp. 61 R3 volume (L) 2.2 2.2 2.2 2.22.2 ES^(R1) (%) 50.0 50.0 60.0 50.0 70 ES^(R2) (%) 50.0 50.0 40.0 50.030 ES^(R3) (%) 0.0 0.0 0.0 0.0 0.0 R1 ethylene 8.6 9.8 11.1 9.1 8.3concentration (wt %) R2 ethylene 12.3 12.3 12.4 13.4 13.0 concentration(wt %) R3 ethylene 12.3 12.3 12.4 13.4 13 concentration (wt %)((1-octene)/ 0.400 0.41 0.4 0.75 1.16 (ethylene))^(R1) (wt/wt)((1-octene)/ 0.00 0.00 0.00 0.00 0.00 (ethylene))^(R2) (wt/wt)(1-octene/ethylene) 0.200 0.205 0.240 0.37 0.817 (wt/wt) (total) OS^(R1)(%) 100 100 100 100 100 OS^(R2) (%) 0 0 0 0 0 OS^(R3) (%) 0 0 0 0 0 H₂^(R1) (ppm) 5.35 5.35 7.21 0.5 0.4 H₂ ^(R2) (ppm) 0.5 0.5 0.54 0.5 0.47H₂ ^(R3) (ppm) 0.0 0.0 0.0 0.0 0.0

TABLE 4C Continuous solution process catalyst parameters for Examples 50through 52 and Comparatives 60 and 61. Process Parameter Example 50Example 51 Example 52 Comp. 60 Comp. 61 R1 total solution rate 393.3345.1 344 439.0 392.2 (kg/h) R2 total solution rate 156.7 204.9 344160.2 107.8 (kg/h) R3 solution rate (kg/h) 0 0 0 0 0 Total solution rate(kg/h) 550 550 688 600 500 R1 feed inlet temp (° C.) 30 30 30 30 35 R2feed inlet temp (° C.) 50 50 50 30 54.9 R3 feed inlet temp(° C.) NA 131131 130 130 R1 catalyst inlet temp 145.1 21.4 24.5 32.2 29.9 (° C.) R2catalyst inlet temp 41.7 30.4 30.4 31.1 40.3 (° C.) R1 Mean temp (° C.)131.8 139.5 154.4 141.0 138.3 R2 Mean temp (° C.) 189.9 189.8 196.0191.0 195.4 R3 exit temp (° C.) 192.7 191.1 180.6 193.0 162.6 Q^(R1) (%)80.0 80.6 80.0 89 89.0 Q^(R2) (%) 85.0 85.0 94.0 79 96.2 Q^((R2+R3)) (%)86.3 86.6 NA 81.5 NA Q^(R3) (%) 8.5 10.4 38.1 12 27.26 Q^(T) (%) 91.892.0 90.8 89.7 93.4

TABLE 5 Physical properties of Examples and Comparatives. PhysicalProperty Example 50 Example 51 Example 52 Comp. 60 Comp. 61 Comp. 67Density (g/cc) 0.9181 0.9172 0.9172 0.9162 0.9193 0.9162 Melt Index, I₂1.02 1.06 0.92 0.96 0.99 0.99 (dg/min) Stress Exponent 1.46 1.45 1.391.30 1.18 1.27 I₁₀/I₂ 10.2 9.91 8.80 7.67 6.22 7.59 MFR, I₂₁/I₂ 43.741.9 30.7 28.5 19.7 30.8 SEC, M_(w) 96695 96238 93004 94536 99753 102603SEC, M_(w)/M_(n) 2.86 2.65 2.04 2.88 2.37 3.08 SEC, M_(z)/M_(w) 2.122.14 1.67 2.15 1.86 2.32 CDBI₅₀ 8.0 6.6 55.4 92.1 62.6 77.5 Branch Freq.16.1 15.8 16.2 13.5 12.1 14.6 (C₆/1000 C) Comonomer 3.2 3.2 3.2 2.7 2.42.9 mole % Ti (ppm) n/a 0.127 0.208 0.303 ± 0.056^(a) Hf (ppm) n/a 0.5300.624 Undetectable^(a) Al (ppm) n/a 4.42 9.05 6.56 ± 1.40^(a) Mg (ppm)n/a 0.165 0.286 0.160 ± 0.089^(a) Cl (ppm) n/a 0.370 0.503 0.496 ±0.038^(a) Internal 0.012 0.012 0.016 0.018 0.020 0.021 Unsaturation/100C Side Chain 0.003 0.002 0.003 0.003 0.000 0.002 Unsaturation/100 CTerminal 0.005 0.005 0.006 0.007 0.006 0.006 Unsaturation/100 C^(a)database average, historical catalyst residues unbridged single sitecatalyst formulation

TABLE 6A Continuous solution process catalyst parameters for Examples 58and 59. Process Parameter Example 58 Example 59 Reactor Mode SeriesSeries R1 Catalyst^(a) (component A) CpF-1 CpF-1 R2 Catalyst^(b) PIC-1PIC-1 R1 catalyst (ppm) 1.08 0.97 R1 ([M^(c)]/[A]) mole ratio 136.0136.1 R1 ([P^(d)]/[M]) mole ratio 0.40 0.40 R1 ([B^(e)]/[A]) mole ratio1.80 1.80 R2 catalyst (ppm) 0.31 1.32 R2 ([M^(c)]/[C]) mole ratio 30.0125.00 R2 ([P^(d)]/[M]) mole ratio 0.30 0.30 R2 ([B^(e)]/[C]) mole ratio1.28 1.27 Prod. Rate (kg/h) 89.7 70.6 ^(a)Catalysts: CpF-1 =[(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]: CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂];PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂], and; PIC-2 = [Cp[(isopropyl)₃PN]TiCl₂].^(b)in-line Ziegler-Natta catalyst formulation ^(c)methylaluminoxane(MMAO-7) ^(d)2,6-di-tert-butyl-4-ethylphenol ^(e)trityltetrakis(pentafluoro-phenyl)borate

TABLE 6B Continuous solution process catalyst parameters for Examples 58and 59. Process Parameter Example 58 Example 59 R3 volume (L) 2.2 2.2ES^(R1) (%) 30 45 ES^(R2) (%) 70 55 ES^(R3) (%) 0 0 R1 ethyleneconcentration (wt %) 8.83 10.18 R2 ethylene concentration (wt %) 15.0214.67 R3 ethylene concentration (wt %) 15.02 14.67((1-octene)/(ethylene))^(R1) (wt/wt) 0.33 0.02 OS^(R1) (%) 50 100OS^(R2) (%) 50 0 OS^(R3) (%) 0 0 H2^(R1) (ppm) 0.22 0.75 H2^(R2) (ppm)30.04 29.99 H2^(R3) (ppm) 0 0

TABLE 6C Continuous solution process catalyst parameters for Examples 58and 59. Process Parameter Example 58 Example 59 R1 total solution rate(kg/h) 268.9 175.6 R2 total solution rate (kg/h) 268.9 175.6 R3 solutionrate (kg/h) 0 0 Total solution rate (kg/h) 537.8 351.2 R1 feed inlettemp (° C.) 30.01 29.82 R2 feed inlet temp (° C.) 29.97 28.88 R3 feedinlet temp(° C.) NA NA R1 catalyst inlet temp (° C.) 145 145 R2 catalystinlet temp (° C.) 30 30 R1 Mean temp (° C.) 135.7 151.9 R2 Mean temp (°C.) 206.1 211.3 Q^(R1) (%) 87.90 91.62 Q^(R2) (%) 81.99 88.07Q^((R2+R3)) (%) 85.72 90.62

TABLE 7 Physical properties of Examples 58 and 59. Physical PropertyExample 58 Example 59 Density (g/cc) 0.9283 0.9440 Melt Index, I₂(dg/min) 4.03 0.24 Stress Exponent 1.85 1.95 I₁₀/I₂ 21.12 n/a MFR,I₂₁/l₂ 142 215.76 SEC, M_(w) 72126 119964 SEC, M_(w)/M_(n) 6.23 10.41SEC, M_(z)/M_(w) 3.68 3.89 CDBI₅₀ 41.1 n/a Branch Freq. (C₆/1000C) 12.64.6 Comonomer mole % 2.5 0.9 Internal Unsaturation/100C 0.010 n/a SideChain Unsaturation/100C 0.006 n/a Terminal Unsaturation/100C 0.009 n/a

TABLE 8 Physical attributes of the first, second and third ethyleneinterpolymer in Example 51, relative to Comparative 67. Example 51Reactor 1 Reactor 2 Reactor 3 Physical Attribute 1^(st) Interpoly 2^(nd)Interpoly 3^(rd) Interpoly Example 51 Weight Percent (%) 49.7 45.3 5.0%100 M_(n) 72856 21935 21935 36278 M_(w) 141247 39575 39575 96238Polydispersity (M_(w)/M_(n)) 1.94 1.80 1.80 2.65 BrF (#C₆/1000C) 30.3^(a) 1.48 ^(g) 1.48 15.8 CDBI₅₀ (%) (range) 85-90 80-95 80-95 6.6Density (g/cm³) 0.8940 ^(b) 0.9413 ^(f) 0.9413 0.9172 Melt Index(dg/min) 0.1 ^(c) 33.9 ^(c) 33.9 1.06 LCBF (dimensionless) 0.0740 ^(d)^(e) ^(e) 0.0368 Comparative 67 Reactor 1 Reactor 2 Reactor 3 PhysicalAttribute 1^(st) Interpoly 2^(nd) Interpoly 3^(rd) Interpoly Comparative67 Weight Percent (%) 47.1 47.9 5% 100 M_(n) 48956 20045 20045 33358M_(w) 165552 35917 25917 102603 Polydispersity (M_(w)/M_(n)) 1.95 1.791.79 3.08 BrF (#C₆/1000C) 12.7 ^(a) 16.3 ^(g) 16.3 14.6 CDBI₅₀ (%)(range) 85-97 80-95 80-95 77.5 Density (g/cm³) 0.9141 ^(b) 0.9181 ^(f)0.9181 0.9162 Melt Index (dg/min) 0.05 ^(c) 49.2 ^(c) 49.2 0.99 LCBF(dimensionless) ^(e) ^(e) ^(e) ^(e) ^(a) BrF (#C₆/100C) = 120.32807 −2.1647891(T^(P) _(CTREF)) + 0.0118658(T^(P) _(CTREF))² − 0.000022(T^(P)_(CTREF))³; where T^(P) _(CTREF) is the peak elution temperature of thefirst ethylene interpolymer in the CTREF chromatogram. ^(b) BrF(#C₆/1000C) = 9341.8 (ρ¹)² − 17766 (ρ¹) + 8446.8, where ρ¹ was thedensity of the first ethylene interpolymer. ^(c) Melt Index (I₂, dg/min)= 5000[1 + (5.7e−5 × Mw)^(2.0)]^(((−4.5−1)/2.0)) + 1.0e−6 where Mw isthe Mw of each slice of a MWD with a weight defined by a (wt. fraction *sigmoid function); where the sigmoid function = 1/(1 + exp(−(logMw −4.2)/0.55)) ^(d) 0.0736 = LCBF^(Example) ⁵¹/(wt^(R1) _(fr)), wherewt^(R1) _(fr) is the weight fraction of the first ethylene interpolymerin Example 51. ^(e) LCBF < 0.0001 (undetectable levels of LCB) ^(f)density of the second and third ethylene interpolymer given the linearspecific volume blending rule and ρ¹, ρ^(f) and weight fractions ^(g)BrF(#C6/1000C) of second and third ethylene interpolymer given linearBrF blending rule and weight fractions

TABLE 9 Blown film processing conditions targeting 1.0 mil (25 μm) filmand output rate of 100 lb/hr, Examples 51 and 52, relative toComparative 67. Process Parameter Units Example 51 Example 52 Comp. 67Density (g/cm³) 0.9172 0.9172 0.9162 Melt Index, I₂ (dg/min) 1.06 0.920.99 Processing Aid^(a) ppm 800 800 800 Output (lbs/hr) lb/hr 100 100100 Melt Temperature ° F. 423 422 472 Extruder Pressure psi 3215 34653818 Extruder Current Amp 30.7 34.2 38 Extruder Voltage Volt 191 182 197Screw Speed Rpm 40 38 41 Nip Roll Speed ft/min 131 131 131 Frost LineHeight In 16 16 16 Specific Output lb/(hr · rpm) 2.5 2.6 2.4 SpecificPower lb/(hr · amp) 3.3 2.9 2.7 Specific Energy W/lb/hr 58.6 62.2 74.1^(a)800 ppm of FX5920A processing aid (available from 3M, St. Paul, MN,USA)

TABLE 10A Blown film physical properties of Examples and Comparatives;film thickness 1.0 mil (25 μm) unless indicated otherwise. PhysicalProperty Units Method Example 51F Example 52F Comp. 67F Density (g/cm³)ASTM D792 0.9172 0.9172 0.9162 Melt Index, I₂ (dg/min) ASTM D1238 1.060.92 0.99 Film Thickness mil Micrometer 1.0 1.0 1.0 Film Hexane wt % 21CFR 0.16 0.21 0.46 Extractables^(a) §177.1520 S.I.T. @ ° C. In-house93.6 89.1 99.1 4.4N/13 mm^(b) Tack Onset @ ° C. In-house 90 86 1011.0N^(b) Max Hot Tack N In-house 3.2 3.62 5.53 Strength^(b) Temperatureat ° C. In-house 105 100 115 Max. Hot Tack^(b) Tear MD g/mil ASTM D1922222 288 282 Tear TD g/mil ASTM D1922 468 568 507 Dart Impact g/mil ASTMD1709 800 449 400 Method A Lubricated J/mm In-house 48 75 81 PunctureGloss at 45° ASTM D2457 26 43 46 Haze % ASTM D1003 32.9 15.9 13.5 ^(a)=3.5 mil film (89 μm) ^(b)= 2.0 mil film (51 μm)

TABLE 10B Blown film physical properties of Examples and Comparatives;film thickness 1.0 mil (25 μm) unless indicated otherwise. PhysicalProperty Units Method Example 51F Example 52F Comp. 67F Density (g/cm³)ASTM D792 0.9172 0.9172 0.9162 Melt Index, I₂ (dg/min) ASTM D1238 1.060.92 0.99 Film Thickness mil Micrometer 1.0 1.0 1.0 1% Sec MPa ASTM D882212 228 164 Modulus MD 1% Sec MPa ASTM D882 255 258 161 Modulus TD 2%Sec MPa ASTM D882 178 190 142 Modulus MD 2% Sec MPa ASTM D882 211 215137 Modulus TD Tensile Break Str MPa ASTM D882 45 48.8 49.7 MD TensileBreak Str MPa ASTM D882 40.4 48.1 29.5 TD Elongation at % ASTM D882 518583 548 Break MD Elongation at % ASTM D882 735 791 665 Break TD TensileYield Str MPa ASTM D882 10.2 10.5 9.1 MD Tensile Yield Str MPa ASTM D88211.4 11.5 8.7 TD Tensile Elong at % ASTM D882 10 10 11 Yield MD TensileElong at % ASTM D882 9 9 10 Yield TD Film Toughness, ft · lb/in³ ASTMD882 1286 1605 1327 Total Energy to Break TD Film Toughness, ft · lb/in³ASTM D882 1528 1870 1105 Avg. Total Energy to Break

TABLE 11A Percent (%) improved SEC weight average molecular weight(M_(w)) at a reactor temperature of 130° C. and 90% ethylene conversionfor the bridged metallocene catalyst formulation relative to theunbridged single site catalyst formulation. Weight % 1- BridgedMetallocene Unbridged Single Site octene in Catalyst FormulationCatalyst Formulation ethylene M_(w) ^(A) M_(w) ^(C) % Improved M_(w)interpolymers Component A (see¹) Component C (see²) (see³) 0.1 CpF-1520658 PIC-1 493848 5.4 2.5 CpF-1 216926 PIC-1 165308 31 5.0 CpF-1179652 PIC-1 130600 38 7.5 CpF-1 160892 PIC-1 113782 41 10.0 CpF-1148783 PIC-1 103179 44 12.5 CpF-1 140021 PIC-1 95641 46 15.0 CpF-1133246 PIC-1 89892 48 17.5 CpF-1 127775 PIC-1 85302 50 20.0 CpF-1 123217PIC-1 81516 51 22.5 CpF-1 119332 PIC-1 78316 52 25.0 CpF-1 115961 PIC-175560 53 27.5 CpF-1 112994 PIC-1 73151 54 30.0 CpF-1 110351 PIC-1 7101955 32.5 CpF-1 107974 PIC-1 69112 56 35.0 CpF-1 105820 PIC-1 67392 5737.5 CpF-1 103852 PIC-1 65830 58 40.0 CpF-1 102045 PIC-1 64401 58 42.5CpF-1 100376 PIC-1 63087 59 45.0 CpF-1 98828 PIC-1 61873 60 ¹M_(w) ^(A)= 278325 × (Octene^(wt %)) − 0.272; where (Octene^(wt %)) is the weight% of octene in the ethylene/1-octene interpolymer ²M_(w) ^(C) = 225732 ×(Octene^(wt %)) − 0.340 ³100% × (M_(w) ^(A) − M_(w) ^(C))/M_(w) ^(C)

TABLE 11B Percent (%) improved SEC weight average molecular weight(M_(w)) at a reactor temperature of 160° C. and 90% ethylene conversionfor the bridged metallocene catalyst formulation relative to theunbridged single site catalyst formulation. Bridged MetalloceneUnbridged Single Site Catalyst Formulation Catalyst Formulation Weight %1-octene in M_(w) ^(A) M_(w) ^(C) % Improved M_(w) ethyleneinterpolymers Component A (see¹) Component C (see²) (see³) 0.1 CpF-1293273 PIC-1 248166 18 2.5 CpF-1 130734 PIC-1 91198 43 5.0 CpF-1 109858PIC-1 73513 49 7.5 CpF-1 99227 PIC-1 64804 53 10.0 CpF-1 92315 PIC-159257 56 12.5 CpF-1 87287 PIC-1 55285 58 15.0 CpF-1 83382 PIC-1 52237 6017.5 CpF-1 80217 PIC-1 49792 61 20.0 CpF-1 77573 PIC-1 47766 62 22.5CpF-1 75314 PIC-1 46048 64 25.0 CpF-1 73348 PIC-1 44564 65 27.5 CpF-171614 PIC-1 43262 66 30.0 CpF-1 70067 PIC-1 42107 66 32.5 CpF-1 68673PIC-1 41072 67 35.0 CpF-1 67408 PIC-1 40136 68 37.5 CpF-1 66251 PIC-139284 69 40.0 CpF-1 65186 PIC-1 38504 69 42.5 CpF-1 64202 PIC-1 37784 7045.0 CpF-1 63287 PIC-1 37119 70 ¹M_(w) ^(A) = 164540 × (Octene^(wt %)) −0.251; where (Octene^(wt %)) is the weight % of octene in theethylene/1-octene interpolymer ²M_(w) ^(C) = 121267 × (Octene^(wt %)) −0.311 ³100% × (M_(w) ^(A) − M_(w) ^(C))/M_(w) ^(C)

TABLE 12A Percent (%) improvement (reduction) in (α-olefin/ethylene)weight ratio in the reactor feed, for the bridged metallocene catalystformulation relative to the unbridged single site catalyst formulation,to produce ethylene interpolymers at the densities shown (130° C.reactor temperature and about 90% ethylene conversion). BridgedMetallocene Unbridged Single Site Weight % 1- Catalyst FormulationCatalyst Formulation % Reduced octene in (α-olefin/ (α-olefin/(α-olefin/ ethylene ethylene)^(A) ethylene)^(C) ethylene) interpolymersComponent A (see¹) Component C (see²) Ratio (see³) 0.0 CpF-1 0.000 PIC-10.00 n/a 2.5 CpF-1 0.0075 PIC-1 0.174 −96% 5.0 CpF-1 0.045 PIC-1 0.422−89% 7.5 CpF-1 0.088 PIC-1 0.690 −87% 10.0 CpF-1 0.136 PIC-1 0.980 −86%12.5 CpF-1 0.188 PIC-1 1.29 −85% 15.0 CpF-1 0.246 PIC-1 1.62 −85% 17.5CpF-1 0.309 PIC-1 1.98 −84% 20.0 CpF-1 0.377 PIC-1 2.35 −84% 22.5 CpF-10.449 PIC-1 2.75 −84% 25.0 CpF-1 0.527 PIC-1 3.17 −83% 27.5 CpF-1 0.610PIC-1 3.60 −83% 30.0 CpF-1 0.698 PIC-1 4.06 −83% 32.5 CpF-1 0.790 PIC-14.55 −83% 35.0 CpF-1 0.888 PIC-1 5.05 −82% 37.5 CpF-1 0.991 PIC-1 5.57−82% 40.0 CpF-1 1.10 PIC-1 6.12 −82% 42.5 CpF-1 1.21 PIC-1 6.68 −82%45.0 CpF-1 1.33 PIC-1 7.27 −82% ¹(α-olefin/ethylene)^(A) = 0.0004 ×(Octene^(wt %))² + 0.0121 × (Octene^(wt %)) − 0.0253; where(Octene^(wt %)) is the weight % of octene in the ethylene/1-octeneinterpolymer ²(α-olefin/ethylene)^(C) = 0.0017 × (Octene^(wt %))² +0.0862 × (Octene^(wt %)) − 0.0517 ³100% × ((α-olefin/ethylene)^(A) −(α-olefin/ethylene)^(C))/(α-olefin/ethylene)^(C)

TABLE 12B Percent (%) improvement (reduction) in (α-olefin/ethylene)weight ratio in the reactor feed, for the bridged metallocene catalystformulation relative to the unbridged single site catalyst formulation,to produce ethylene interpolymers at the densities shown (160° C.reactor temperature and about 90% ethylene conversion). BridgedMetallocene Unbridged Single Site % Reduced Weight % 1- CatalystFormulation Catalyst Formulation (α-olefin/ octene in (α-olefin/(α-olefin/ ethylene) ethylene ethylene)^(A) ethylene)^(C) Ratiointerpolymers Component A (see¹) Component C (see²) (see³) 0.0 CpF-10.00 PIC-1 0.00 n/a 2.5 CpF-1 0.0078 PIC-1 0.183 −96% 5.0 CpF-1 0.031PIC-1 0.407 −92% 7.5 CpF-1 0.066 PIC-1 0.653 −90% 10.0 CpF-1 0.112 PIC-10.920 −88% 12.5 CpF-1 0.170 PIC-1 1.21 −86% 15.0 CpF-1 0.238 PIC-1 1.52−84% 17.5 CpF-1 0.318 PIC-1 1.85 −83% 20.0 CpF-1 0.409 PIC-1 2.20 −81%22.5 CpF-1 0.512 PIC-1 2.57 −80% 25.0 CpF-1 0.625 PIC-1 2.97 −79% 27.5CpF-1 0.750 PIC-1 3.39 −78% 30.0 CpF-1 0.886 PIC-1 3.82 −77% 32.5 CpF-11.03 PIC-1 4.28 −76% 35.0 CpF-1 1.19 PIC-1 4.76 −75% 37.5 CpF-1 1.36PIC-1 5.26 −74% 40.0 CpF-1 1.54 PIC-1 5.78 −73% 42.5 CpF-1 1.74 PIC-16.33 −73% 45.0 CpF-1 1.94 PIC-1 6.89 −72% ¹(α-olefin/ethylene)^(A) =0.0009 × (Octane^(wt %))² + 0.0027 × (Octene^(wt %)) − 0.0046; where(Octene^(wt %)) is the weight % of octene in the ethylene/1-octeneinterpolymer ²(α-olefin/ethylene)^(C) = 0.0017 × (Octene^(wt %))² +0.0771 × (Octene^(wt %)) − 0.0208 ³100% × ((α-olefin/ethylene)¹ −(α-olefin/ethylene)^(C)/(α-olefin/ethylene)^(C)

TABLE 13 CPU continuous solution phase, one reactor, ethylenehomopolymerization using the bridged metallocene catalyst formulation.Polymerization Temp. (° C.) 130 160 190 Sample Code Example C1 ExampleC2 Example C3 Example C4 Example C5 Example C6 Component A¹ 0.15 0.470.19 0.82 0.22 0.93 Concentration in Reactor [mM/L] ([M]/[A]) 100 100100 100 100 100 mole ratio ([P]/[M]) 0.40 0.40 0.40 0.40 0.40 0.40 moleratio ([B]/[A]) 1.20 1.20 1.20 1.20 1.20 1.20 mole ratio HUT^(CPU) (min)119 119 109 109 99 99 Q^(CPU) (%) 74.5 94.2 74.9 94.4 75.5 94.8 K_(p)^(CPU) 12731 22328 11727 15704 13116 17761 (L/(mM · min) ¹CpF-2 =[(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]

TABLE 14 13C-NMR determined long chain branching (LCB) in the firstethylene interpolymer (ethylene homopolymer) produced using the bridgedmetallocene catalyst formulation¹ on the CPU. Sample Example C10 ExampleC11 Example C12 Example C13 Example C14 Example C15 CPU Reactor 190 190160 160 130 130 Temp. (° C.) CPU Ethylene 95.6 85.3 95.0 75.3 93.6 85.1Conversion (wt %) CPU [ethylene] 0.62 2.10 0.57 2.80 0.53 1.23 out (wt.%) ¹³C 0.23 0.09 0.09 0.03 0.07 0.03 LCB/1000 C GPC M_(w) (g/mol) 4633793368 107818 255097 234744 305005 Pd (M_(w)/M_(n)) 1.88 1.88 1.85 1.92.02 2.29 ¹³C-NMR, 2.37 1.68 1.64 0.98 0.94 0.73 C1/1000 C ¹³C-NMR, 0.20.14 0.17 0.10 0.12 0.09 C2/1000 C ¹³C-NMR, 0.08 0.05 0.05 D² D DC3/1000 C ¹³C-NMR, 0.07 0.05 0.05 D D D C4/1000 C ¹³C-NMR, 0.3 0.12 0.12D 0.07 D (C6 + LCB)/1000 C ¹³C-NMR, 1.1 0.52 0.47 0.22 0.23 0.21Sat.Term./1000 C M_(n) (g/mol) 24640 49615 58131 118329 116035 133001M_(z) (g/mol) 73219 152320 176254 383637 447833 567658 I₂ (dg/min) 16.6n/a 0.15 n/a n/a n/a I₂₁ (dg/min) 380 n/a 10 0.54 0.53 0.12 I₂₁/I₂ 22.9n/a 66.1 n/a n/a n/a ¹Component A = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] D =detectable but not quantifiable

What is claimed is:
 1. An ethylene interpolymer product comprising: (i)a first ethylene interpolymer; (ii) a second ethylene interpolymer; and(iii) optionally a third ethylene interpolymer; wherein the ethyleneinterpolymer product has a dimensionless Long Chain Branching Factor,LCBF, greater than or equal to about 0.001; wherein the ethyleneinterpolymer product has from about 0.0015 parts per million (ppm) toabout 2.4 ppm of hafnium, and; wherein the ethylene interpolymer producthas from about 0.006 ppm to about 5.7 ppm of titanium.
 2. The ethyleneinterpolymer product according to claim 1, further comprising one ormore of the following: (i) less than or equal to about 0.01 terminalvinyl unsaturations per 100 carbon atoms; (ii) from about 0.03 ppm toabout 6.0 ppm of a total catalytic metal.
 3. The ethylene interpolymerproduct according to claim 1 having a melt index from about 0.3 to about500 dg/minute; wherein melt index is measured according to ASTM D1238(2.16 kg load and 190° C.).
 4. The ethylene interpolymer productaccording to claim 1 having a density from about 0.855 g/cm³ to about0.975 g/cm³; wherein density is measured according to ASTM D792.
 5. Theethylene interpolymer product according to claim 1 having a M_(w)/M_(n)from about 1.7 to about
 25. 6. The ethylene interpolymer productaccording to claim 1 having a CDBI₅₀ from about 1% to about 98%.
 7. Theethylene interpolymer product according to claim 1 wherein: (i) thefirst ethylene interpolymer is from about 5 to about 60 weight percentof the ethylene interpolymer product; (ii) the second ethyleneinterpolymer is from about 20 to about 95 weight percent of the ethyleneinterpolymer product, and; (iii) optionally the third ethyleneinterpolymer is from about 0 to about 30 weight percent of the ethyleneinterpolymer product; wherein weight percent is the weight of the firstethylene interpolymer, the second ethylene interpolymer, or the optionalthird ethylene interpolymer, individually, divided by the weight of theethylene interpolymer product.
 8. The ethylene interpolymer productaccording to claim 1 wherein: (i) the first ethylene interpolymer has amelt index from about 0.01 to about 200 dg/minute; (ii) the secondethylene interpolymer has melt index from about 0.3 to about 1000dg/minute, and; (iii) optionally the third ethylene interpolymer has amelt index from about 0.5 to about 2000 dg/minute; wherein melt index ismeasured according to ASTM D1238 (2.16 kg load and 190° C.).
 9. Theethylene interpolymer product according to claim 1 wherein: (i) thefirst ethylene interpolymer has a density from about 0.855 g/cm³ toabout 0.975 g/cm³; (ii) the second ethylene interpolymer has a densityfrom about 0.855 g/cm³ to about 0.975 g/cm³, and; (iii) optionally thethird ethylene interpolymer has density from about 0.855 g/cm³ to about0.975 g/cm³; wherein density is measured according to ASTM D792.
 10. Theethylene interpolymer product according to claim 1 manufactured in asolution polymerization process.
 11. The ethylene interpolymer productaccording to claim 1, further comprising from 0 to about 10 mole percentof one or more α-olefin.
 12. The ethylene interpolymer product accordingto claim 11, wherein the one or more α-olefin are C₃ to C₁₀ α-olefins.13. The ethylene interpolymer product according to claim 11, wherein theone or more α-olefin is 1-hexene, 1-octene or a mixture thereof.
 14. Theethylene interpolymer product according to claim 1, wherein the firstethylene interpolymer is produced using at least one homogeneouscatalyst formulation.
 15. The ethylene interpolymer product according toclaim 13, wherein the first ethylene interpolymer is produced using afirst homogeneous catalyst formulation.
 16. The ethylene interpolymerproduct according to claim 15, wherein the first homogeneous catalystformulation is a bridged metallocene catalyst formulation.
 17. Theethylene interpolymer product according to claim 16, wherein the bridgedmetallocene catalyst formulation comprises a component A defined byFormula (I)

wherein M is a metal selected from titanium, hafnium, and zirconium; Gis the element carbon, silicon, germanium, tin, or lead; X represents ahalogen atom each R₆ group is independently selected from a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀aryl oxide radical, these radicals may be linear, branched or cyclic orfurther substituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀alkoxy radicals, C₆₋₁₀ aryl, or aryloxy radicals; R₁ is a hydrogen atom,a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀ aryloxide radical; R₂ and R₃ are independently selected from a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀aryl oxide radical; and R₄ and R₅ are independently selected from ahydrogen atom, a C₁₋₂₀ hydrocarbyl radial, a C₁₋₂₀ alkoxy radical, or aC₆₋₁₀ aryl oxide radical.
 18. The ethylene interpolymer productaccording to claim 17, wherein the second ethylene interpolymer isproduced using at least one homogeneous catalyst formulation.
 19. Theethylene interpolymer product according to claim 17, wherein the secondethylene interpolymer is produced using a second homogeneous catalystformulation.
 20. The ethylene interpolymer product according to claim19, wherein the second homogeneous catalyst formulation is an unbridgedsingle site catalyst formulation.
 21. The ethylene interpolymer productaccording to claim 20, wherein said unbridged single site catalystformulation comprises a component C defined by Formula (II)(L^(A))_(a)M(Pl)_(b)(Q)_(n)   (II) wherein M is a metal selected fromtitanium, hafnium, and zirconium; L^(A) is selected from the groupconsisting of unsubstituted cyclopentadienyl, substitutedcyclopentadienyl, unsubstituted indenyl, substituted indenyl,unsubstituted fluorenyl, and substituted fluorenyl; Pl is aphosphinimine ligand; Q is independently selected from the groupconsisting of a hydrogen atom, a halogen atom, a C₁₋₁₀ hydrocarbylradical, a C₁₋₁₀ alkoxy radical, and a C₅₋₁₀ aryl oxide radical, whereineach of the hydrocarbyl, alkoxy, and aryl oxide radicals may beunsubstituted or further substituted by a halogen atom, a C₁₋₁₈ alkylradical, a C₁₋₈ alkoxy radical, a C₆₋₁₀ aryl, or aryloxy radical, anamido radical which is unsubstituted or substituted by up to two C₁₋₈alkyl radicals, or a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; wherein a is 1; b is 1; nis 1 or 2; and (a+b+n) is equivalent to the valence of the metal M. 22.The ethylene interpolymer product according to claim 20, wherein thethird ethylene interpolymer is produced using a fifth homogeneouscatalyst formulation and/or a heterogeneous catalyst formulation. 23.The ethylene interpolymer product according to claim 22, wherein thefifth homogeneous catalyst formulation is the bridged metallocenecatalyst formulation, the unbridged single site catalyst formulation, ora fourth homogeneous catalyst formulation; wherein the fourthhomogeneous catalyst formulation comprises a bulky ligand-metal complexthat is not a member of the genera defined by Formula (I) or Formula(II).
 24. The ethylene interpolymer product according to 22, wherein theheterogeneous catalyst formulation is an in-line Ziegler-Natta catalystformulation or a batch Ziegler-Natta catalyst formulation.
 25. Theethylene interpolymer product according to claim 16, wherein theethylene interpolymer product contains ≤2.4 ppm of a catalytic metal A,wherein the catalytic metal A originates from the bridged metallocenecatalyst formulation.
 26. The ethylene interpolymer product of claim 25,wherein the catalytic metal A is hafnium.
 27. The ethylene interpolymerproduct according to claim 20, wherein the ethylene interpolymer productcontains ≤2.9 ppm of a catalytic metal C, wherein the catalytic metal Coriginates from the unbridged single site catalyst formulation.
 28. Theethylene interpolymer product of claim 27, wherein the catalytic metal Cis titanium.
 29. The ethylene interpolymer product according to claim23, wherein the ethylene interpolymer product contains ≤1 ppm of acatalytic metal D, wherein the catalytic metal D originates from thefourth homogeneous catalyst formulation.
 30. The ethylene interpolymerproduct of claim 29, wherein the catalytic metal D is titanium,zirconium, or hafnium.
 31. The ethylene interpolymer product accordingto claim 22, wherein said ethylene interpolymer product contains ≤3.6ppm of a catalytic metal Z; wherein the catalytic metal Z originatesfrom the heterogeneous catalyst formulation.
 32. The ethyleneinterpolymer product of claim 31 wherein the catalytic metal Z istitanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium,or osmium.
 33. The ethylene interpolymer product according to claim 1,wherein the first ethylene interpolymer has a first M_(w)/M_(n) fromabout 1.7 to about 2.8, the second ethylene interpolymer has a secondM_(w)/M_(n) from about 1.7 to about 2.8, and the optional third ethyleneinterpolymer has a third M_(w)/M_(n) from about 1.7 to about 5.0. 34.The ethylene interpolymer product according to claim 1, wherein thefirst ethylene interpolymer has a first CDBI₅₀ from about 70 to about98%, the second ethylene interpolymer has a second CDBI₅₀ from about 70to about 98% and the optional third ethylene interpolymer has a thirdCDBI₅₀ from about 35 to about 98%.
 35. The ethylene interpolymer productaccording to claim 1, wherein the ethylene interpolymer product has aCDBI₅₀ from about 1 to about 98%.
 36. A continuous solutionpolymerization process S comprising: i) injecting ethylene, a processsolvent, a first homogeneous catalyst formulation, optionally one ormore α-olefins, and optionally hydrogen into a first reactor to producea first exit stream containing a first ethylene interpolymer in theprocess solvent; ii) passing the first exit stream into a second reactorand injecting into the second reactor ethylene, the process solvent, asecond homogeneous catalyst formulation, optionally one or moreα-olefins, and optionally hydrogen to produce a second exit streamcontaining a second ethylene interpolymer and the first ethyleneinterpolymer in the process solvent, and optionally adding a catalystdeactivator A to the second exit stream, downstream of the secondreactor, forming a deactivated solution A; iii) passing the second exitstream or the deactivated solution A into a third reactor and optionallyinjecting into the third reactor ethylene, a/the process solvent, one ormore α-olefins, hydrogen, and a fifth homogeneous catalyst formulationand/or a heterogeneous catalyst formulation to produce a third exitstream containing an optional third ethylene interpolymer, the secondethylene interpolymer, and the first ethylene interpolymer in theprocess solvent; iv) optionally adding a catalyst deactivator B to thethird exit stream, downstream of the third reactor, forming adeactivated solution B; with the proviso that step iv) is skipped if thecatalyst deactivator A was added in step ii); v) optionally adding apassivator to the deactivated solution A or B forming a passivatedsolution, with the proviso that step v) is skipped if the heterogeneouscatalyst formulation was not added to the third reactor; and vi) phaseseparating the deactivated solution A or B or the passivated solution torecover the ethylene interpolymer product; or a continuous solutionpolymerization process P comprising: a) injecting ethylene, a processsolvent, a first homogeneous catalyst formulation, optionally one ormore α-olefins, and optionally hydrogen into a first reactor to producea first exit stream containing a first ethylene interpolymer in theprocess solvent; b) injecting ethylene, the process solvent, a secondhomogeneous catalyst formulation, optionally one or more α-olefins, andoptionally hydrogen into a second reactor to produce a second exitstream containing a second ethylene interpolymer in the process solvent;c) combining the first and the second exit streams to form a third exitstream and optionally adding a catalyst deactivator C to the third exitstream to form a deactivated solution C; d) passing the third exitstream or the deactivated solution C into a third reactor and optionallyinjecting into the third reactor ethylene, process solvent, one or moreα-olefins, hydrogen, and a fifth homogeneous catalyst formulation and/ora heterogeneous catalyst formulation to produce a fourth exit streamcontaining an optional third ethylene interpolymer, the second ethyleneinterpolymer, and the first ethylene interpolymer in said processsolvent; e) optionally adding a catalyst deactivator D to the fourthexit stream, downstream of said the reactor, forming a deactivatedsolution D, with the proviso that step e) is skipped if the catalystdeactivator C was added in step c); f) optionally adding a passivator tothe deactivated solution C or D forming a passivated solution, with theproviso that step f) is skipped if the heterogeneous catalystformulation was not added to the third reactor; and g) phase separatingthe deactivated solution C or D or the passivated solution to recoverthe ethylene interpolymer product; wherein, the continuous solutionpolymerization process S or P is improved by having one or more of thefollowing: (I) at least a 70% reduced [α-olefin/ethylene] weight ratioas defined by the following formula:${\%\mspace{14mu}{{Reduced}\left\lbrack \frac{\alpha\text{-}{olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight ofthe α-olefin added to the first reactor by the weight of the ethyleneadded to the first reactor, wherein the first ethylene interpolymerhaving a target density is produced by the first homogeneous catalystformulation; and (α-olefin/ethylene)^(C) is calculated by dividing theweight of the α-olefin added to the first reactor by the weight of theethylene added to the first reactor, wherein a control ethyleneinterpolymer having the target density is produced by replacing thefirst homogeneous catalyst formulation with a the homogeneous catalystformulation; (II) at least a 5% improved weight average molecular weightas defined by the following formula:% Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5% whereinM_(w) ^(A) is the weight average molecular weight of the first ethyleneinterpolymer and M_(w) ^(C) is a weight average molecular weight of acomparative ethylene interpolymer; wherein the comparative ethyleneinterpolymer is produced in the first reactor by replacing the firsthomogeneous catalyst formulation with the third homogeneous catalystformulation.
 37. An ethylene interpolymer product produced using acontinuous solution polymerization process comprising: (i) from about 5weight percent to about 60 weight percent of a first ethyleneinterpolymer having a melt index from about 0.01 g/10 minutes to about200 g/10 minutes and a target density from about 0.855 g/cm³ to about0.975 g/cm³; (ii) from about 20 weight percent to about 95 weightpercent of a second ethylene interpolymer having a melt index from about0.3 g/10 minutes to about 1000 g/10 minutes and a density from about0.855 g/cm³ to about 0.975 g/cm³; (iii) optionally from about 0 weightpercent to about 30 weight percent of a third ethylene interpolymerhaving a melt index from about 0.5 g/10 minutes to about 2000 g/10minutes and a density from about 0.855 g/cm³ to about 0.975 g/cm³; and(iv) a means for reducing by at least −70% an [α-olefin/ethylene] weightratio required to produce the first ethylene interpolymer having saidtarget density, wherein the reduction in the [α-olefin/ethylene] weightratio is defined by the following formula:${\%\mspace{14mu}{{Reduced}\left\lbrack \frac{\alpha\text{-}{olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha\text{-}{olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight ofone or more α-olefins added to a first reactor by the weight of ethyleneadded to the first reactor, wherein the first ethylene interpolymerhaving the target density is produced using a bridged metallocenecatalyst formulation; and (α-olefin/ethylene)^(C) is calculated bydividing the weight of the one or more α-olefin added to the firstreactor by the weight of the ethylene added to the first reactor,wherein a control ethylene interpolymer having the target density isproduced by replacing the bridged metallocene catalyst formulation withan unbridged single site catalyst formulation; wherein the ethyleneinterpolymer product is characterized as having a melt index from about0.3 g/10 minutes to about 500 g/10 minutes, a density from about 0.855g/cm³ to about 0.975 g/cm³, a M_(w)/M_(n) from about 1.7 to about 25,and a CDBI₅₀ from about 1% to about 98% a dimensionless Long ChainBranching Factor, LCBF, greater than or equal to about 0.001, from about0.0015 ppm to about 2.4 ppm of hafnium, and from about 0.006 ppm toabout 5.7 ppm of titanium; wherein melt index is measured according toASTM D1238 (2.16 kg load and 190° C.), density is measured according toASTM D792 and weight percent is the weight of the first, the second, orsaid optional third ethylene polymer, individually, divided by theweight of said ethylene interpolymer product.
 38. A polyethylene filmcomprising at least one layer, wherein the layer comprises at least oneethylene interpolymer product comprising: (i) a first ethyleneinterpolymer; (ii) a second ethylene interpolymer; and (iii) optionallya third ethylene interpolymer; wherein the ethylene interpolymer producthas a dimensionless Long Chain Branching Factor, LCBF, greater than orequal to about 0.001; wherein the ethylene interpolymer product has fromabout 0.0015 ppm to about 2.4 ppm of hafnium, and; wherein the ethyleneinterpolymer product has from about 0.006 ppm to about 5.7 ppm oftitanium.
 39. An ethylene interpolymer product produced using acontinuous solution polymerization process comprising: from about 5weight percent to about 60 weight percent of a first ethyleneinterpolymer having a melt index from about 0.01 g/10 minutes to about200 g/10 minutes and a target density from about 0.855 g/cm³ to about0.975 g/cm³; (ii) from about 20 weight percent to about 95 weightpercent of a second ethylene interpolymer having a melt index from about0.3 g/10 minutes to about 1000 g/10 minutes and a density from about0.855 g/cm³ to about 0.975 g/cm³; (iii) optionally from about 0 weightpercent to about 30 weight percent of a third ethylene interpolymerhaving a melt index from about 0.5 g/10 minutes to about 2,000 g/10minutes and a density from about 0.855 g/cm³ to about 0.975 g/cm³; and(iv) a means for improving by at least 5% a weight average molecularweight (M_(w)), wherein the % Improved M_(w) is defined by the followingformula% Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5% whereinM_(w) ^(A) is the weight average molecular weight of the first ethyleneinterpolymer produced using a bridged metallocene catalyst formulationin a first reactor and M_(w) ^(C) is a weight average molecular weightof a comparative ethylene interpolymer having the target densityproduced by replacing the bridged metallocene catalyst formulation inthe first reactor with an unbridged single site catalyst formulation;wherein the ethylene interpolymer product is characterized as having amelt index from about 0.3 g/10 minutes to about 500 g/10 minutes, adensity from about 0.855 g/cm³ to about 0.975 g/cm³, a M_(w)/M_(n) fromabout 1.7 to about 25, and a CDBI₅O from about 1% to about 98%, adimensionless Long Chain Branching Factor, LCBF, greater than or equalto about 0.001, from about 0.0015 ppm to about 2.4 ppm of hafnium, andfrom about 0.006 ppm to about 5.7 ppm of titanium; wherein melt index ismeasured according to ASTM D1238 (2.16 kg load and 190° C.), density ismeasured according to ASTM D792, and weight percent is the weight of thefirst, the second or the optional third ethylene polymer, individually,divided by the weight of the ethylene interpolymer product.